Philippe Coutinho, who struggled to impress for Barcelona during the 2018-19 campaign, scored twice in the space of three second-half minutes before Everton netted a stunner for the host nation late on.
In truth, it was always going to be a straightforward start to their Group A campaign for Tite's outfit against a Bolivia side that entered the competition as the lowest-ranked CONMEBOL team.
Neymar's absence for the hosts could prove vital later in the competition. Tite was still able to select an XI full of talent, though, with Everton's Richarlison given the chance to impress alongside David Neres and Roberto Firmino in the final third of the field.
Richarlison was extremely bright in the early moments and won his team a free kick in the third minute after showing quick feet in a tight position, but the resultant effort from Coutinho was straight into the wall.
The pressure was relentless in the early stages and the Selecao had another opportunity in the 11th minute when Thiago Silva climbed highest inside the Bolivia box, but the centre-back's header just dropped wide of the far post.
VAR was used for the first time in the 21st minute when Fernando Saucedo lunged into a challenge with Casemiro, which ultimately led to the Bolivia midfielder picking up the first yellow card of the tournament.
Bolivia goalkeeper Lampe had a nervy moment in the 30th minute when a loose clearance fell for Richarlison, but Adrian Jusino was on hand to make a smart block as Eduardo Villegas's team continued to defend well.
Thiago Silva headed over the Bolivia crossbar 10 minutes before the break as the host nation continued to threaten, before Casemiro just dropped an attempt wide of the post late in the first period.
The underdogs held firm, however, to leave the two teams level entering the half-time interval. Brazil had 76% possession in the opening 45 minutes - only one shot on target arrived from Tite's side, though, which was an indication of their struggles in the final third of the field.
Brazil were awarded a penalty early in the second half following a VAR review, however, with Jusino being penalised for handball inside the box. Coutinho stepped forward for the host nation and expertly found the bottom corner to make the breakthrough in Sao Paulo, much to the relief of the majority inside the stadium.
Three minutes later, Brazil had their second and it was Coutinho once again, with the Barcelona attacker heading a Firmino cross into the back of the net from close range.
Tite made his first alteration of the match in the 65th minute, with Gabriel Jesus sent onto the field. Bolivia, meanwhile, also changed two players in the period that followed the second goal, which all but decided the contest.
Neres was causing Bolivia all sorts of problems as the second period approached its latter stages. Clear chances were few and far between, though, and Brazil's number seven saw his night end in the 81st minute when Everton was introduced in the final third of the field.
It did not take long for Everton to make his mark, with the 23-year-old driving down the left before cutting onto his right foot and picking out the far corner of the net to score a wonderful third for Brazil in the 85th minute.
The Selecao have not won the Copa America since 2007 but are considered to be the favourites this summer, particularly considering that home advantage is also with Tite's team.
Next up for Brazil is a clash with Venezuela on Tuesday night, while Bolivia will be looking to bounce back from the defeat when they face Peru.
BRAZIL (4-3-3): Alisson, Alves, Marquinhos, Thiago Silva, Luis; Casemiro, Fernandinho, Coutinho; Richarlison (Willian 83'), Firmino (Jesus 65'), Neres (Everton 81')
BOLIVIA (4-4-1-1): Lampe; D Bejarano, Haquin, Jusino, M Bejarano; Chumacero, Justiniano, Saucedo (Wayar 59'), Saavedra (Vaca 64'); Castro (Ramallo 75'); Martins