The two teams have been drawn in Group E alongside Albion Rovers, Ayr United and Falkirk and will be looking to improve on last season's performances in this competition, after failing to progress to the knockout rounds a year ago.
Edinburgh City head into the 2021-22 campaign off the back of losing 3-2 on aggregate in the League One playoff final against Dumbarton in May.
In a shortened 22-game season – due to the coronavirus pandemic – the Citizens finished second in the fourth tier of Scottish football behind champions Queen's Park, but manager Gary Naysmith is hoping his side can brush aside their playoff heartache this term and go one better by clinching promotion from League Two.
Naysmith's primary focus now, however, is the League Cup, with four group stage matches in 13 days to prepare for, before their league campaign begins against Albion Rovers later this month.
The Citizens have had mixed results from their three pre-season friendlies in the last week, losing 3-1 to Gala Fairydean Rovers, drawing 1-1 against Bonnyrigg Rose and winning 1-0 at Rangers Colts.
Edinburgh City have lost both of their previous two competitive meetings against Hamilton, conceding nine goals in the process, but a win for Friday's hosts would be a great way for Naysmith's men to kick off the new campaign, as they look to progress from the group stage for the first time in their history.
Unlike Edinburgh City, Hamilton have not played any pre-season friendlies, with their last fixture being a 2-0 defeat against Kilmarnock in May, a result that confirmed their relegation from the Scottish Premiership.
The Accies finished bottom of the table, winning just seven of their 38 league matches, and were demoted to the second tier for the first time in seven years.
Manager Brian Rice is tasked with guiding Hamilton back to the top-flight at the first attempt, with the core group of players that he had last season still currently with the club.
Rice's side failed to progress from the League Cup group stages last year, but they will fancy their chances of reaching the knockout rounds this campaign, after being handed a favourable draw in Group E.
Hamilton have won both of their previous two meetings against Edinburgh City, winning by an aggregate score of 9-2. Their last encounter was a comfortable 5-0 Scottish Cup victory in January 2020.
New recruits James Hilton and Michael McFarlane may feature on the flanks, while attacking midfielder Danny Handling is set to start in behind forward Ouzy See, who scored in their last pre-season friendly.
As for Hamilton, Rice used a back three for the majority of last season and he is expected to stick with this system on Friday.
Edinburgh City possible starting lineup:
Goodfellow; Kidd, Hamilton, Reekie, McIntyre; Tapping, Jardine; Hilton, Handling, McFarlane; See
Hamilton Academical possible starting lineup:
Fulton; Hamilton, Want, Easton; Hodson, Odoffin, Martin, McMann; Mimnaugh; Moyo, Ryan
We say: Edinburgh City 1-2 Hamilton Academical
Both sides will be hoping to bounce back after disappointing ends to their respective campaigns last season with three points in their opening League Cup match on Friday. Hamilton will be the favourites to win at Ainslie Park, though, and we expect them to secure a narrow victory.