Besiktas vs. Dortmund (Wednesday, 5.45pm)
The hosts sit at the summit of the Turkish top flight after four domestic games and earned automatic qualification for Europe's elite competition by winning the Super Lig title last season, while the German outfit will look to build on last year's Champions League campaign, as they reached the quarter-finals.
We say: Besiktas 1-3 Borussia Dortmund
Given Borussia Dortmund's impressive threat going forward and defensive frailties, we think this is bound to be a high-scoring affair, and we give the edge to the German side.
Haaland has carried his fine form into the new season, and if he continues at the rate he is currently going at, the Norwegian forward should fire his side to an opening victory in Turkey.
Sheriff Tiraspol vs. Shakhtar (Wednesday, 5.45pm)
Two sides who battled through Champions League qualification to reach the 2021-22 group stage will lock horns on Wednesday evening, when tournament debutants Sheriff Tiraspol welcome Shakhtar Donetsk to the Bolshaya Sportivnaya Arena.
This will be the third meeting between the two teams in a European competition, with the Ukrainian side going unbeaten in their previous two matches during the 2003-04 Champions League qualifiers.
We say: Sheriff Tiraspol 0-2 Shakhtar Donetsk
Both Sheriff and Shakhtar like to play an attractive brand of football and so an entertaining game could be on the cards in Transnistria.
The visitors will be the favourites on Wednesday night and we expect them to secure a routine win against the Champions League debutants.
Man City vs. RB Leipzig (Wednesday, 8.00pm)
The hosts fell at the final hurdle to Chelsea in the 2020-21 final, whereas Leipzig were swiftly dispatched by Liverpool in the last 16.
We say: Manchester City 3-1 RB Leipzig
In spite of their struggles, Leipzig have attacking quality in abundance, and we would not put it past Marsch's side to break the defensive resilience of the Premier League champions.
However, City have enjoyed a far superior start to the season and have their eyes firmly on the prize this time around, so we can only back Guardiola's men to get the job done convincingly.
Brugge vs. PSG (Wednesday, 8.00pm)
The Belgian giants head into the daunting group as rank outsiders for a top-two finish, while PSG will finally seek the European crown that has eluded them for so long.
We say: Club Brugge 0-3 Paris Saint-Germain
The prospect of facing Messi, Mbappe and Neymar would strike fear into the hearts of any defence, let alone a Brugge side who shipped six goals to Gent only two weeks ago.
It would be harsh to label the hosts as whipping boys in Group A, but Pochettino's men ought to show their class and march to a resounding opening success in the Champions League.
Atletico vs. Porto (Wednesday, 8.00pm)
Diego Simeone's side enter the game having claimed a 2-1 win over Espanyol in La Liga action at the weekend, while Porto played out a 1-1 draw with Primeira Liga champions Sporting Lisbon.
We say: Atletico Madrid 2-0 Porto
The loss of an experienced head in Savic is obviously a bitter blow for Atletico, but their ability to grind out narrow results when it matters most is almost unparalleled.
Porto have started the Primeira Liga season in ideal fashion but will struggle to break down a typically robust Simeone defence, so we can only back Atletico to get off on the right foot here.
Liverpool vs. AC Milan (Wednesday, 8.00pm)
In a repeat of the 2005 and 2007 Champions League finals, Liverpool and AC Milan kick off the 2021-22 edition with a mouthwatering affair at Anfield on Wednesday.
The Reds go in search of their seventh European crown this year, while Milan are aiming to come up trumps on the continental stage for the eighth time.
We say: Liverpool 1-1 AC Milan
With both of these European giants making fast starts to their domestic title challenges and seeking to carry that momentum over to continental competition, a tense and closely-fought affair should be in store on Merseyside.
There may be brief but well-documented history between Liverpool and AC Milan in the Champions League, but we are struggling to see either side gaining the upper hand and are backing a score draw in Wednesday's opener.
Sporting Lisbon vs. Ajax (Wednesday, 8.00pm)
Sporting Lisbon and Ajax will kick off their Champions League campaigns on Wednesday, when they clash in the Portuguese capital.
The two sides won the Portuguese and Dutch top flights respectively last year, and will both be keen to get off the mark at the first time of asking.
We say: Sporting Lisbon 1-2 Ajax
We certainly see this being a closely-fought encounter, between two sides who excelled on the domestic scene last season.
Given Sporting could be playing without both their key centre-back and key attacker, we give the narrow edge to the visitors, as they arrive in Lisbon at somewhat of a good time, although it will certainly not be a routine victory for ten Hag's men.
Inter Milan vs. Real Madrid (Wednesday, 8.00pm)
This is the second consecutive campaign in which these two European giants, along with Ukrainian outfit Shakhtar Donetsk, have been drawn in the same group of the competition; Los Blancos beat the Nerazzurri home and away last season, including a 2-0 victory in Milan.
We say: Inter Milan 1-2 Real Madrid
Even though Inter have had success on home soil against Real Madrid, last season's encounter with the Spanish giants proved to be a challenge and another difficult game could be on the cards on Wednesday.
We expect goals from this blockbuster clash at the San Siro, though Ancelotti's men should have enough to take away all three points.