Neymar, who also withstood a few challenges in the game, received the ball from midfielder Philippe Coutinho in the 68th and dribbled past Croatia defenders Sime Vrsaljko and Duje Caleta-Car.
The Paris Saint-Germain striker replaced Fernandinho at half-time, and put Brazil in front in the 69th minute.
Indeed, Croatia had arguably the better of the chances before Neymar produced his moment of magic, collecting Coutinho's pass and dancing into space before finishing from close range in his first appearance since surgery on a broken foot.
Xbox Games with Gold for June Revealed
Sonic & All-Stars Racing Transformed will be available for the Xbox 360 on June 1st and will remain available until June 15th. Thankfully, despite no announcements from Microsoft , the list of Games with Gold for the month of June has just been leaked.
Brazil head to Russian Federation as one of the favourites but this was a largely flat display, despite Tite choosing to start Gabriel Jesus, Willian and Philippe Coutinho, making his first appearance at the stadium since leaving Liverpool for Barcelona in January.
Roberto Firmino added a second in stoppage time to satisfy the home fans on Merseyside.
Brazil and Croatia are in Liverpool as they prepare for the World Cup later this month.
Just 98 days after suffering an injury he feared would keep him out of the upcoming World Cup in Russia, Neymar was back with a bang at Anfield.
Hire Zinedine Zidane and sign Cristiano Ronaldo says Stan Collymore
He had been an assistant to Carlo Ancelotti when Madrid won the Champions League in 2014. "When I took the decision that was it". I will be around, close to this club all my life but the decision, maybe for many doesn't make any sense, for me it makes sense.
"Neymar is going to have ups and downs like he had in training until the third, fourth game (on his return)".
The press successful negated much of Brazil's play in the first half with usually marauding left-back Marcelo stuck playing long balls at times to switch the play out to Willian.
At the same time, Rakitic pushed forward so that Croatia were practically playing a 4-1-3-2 when off the ball, with all five of the attacking players spread to cut down the passing options for Brazil's defenders.
The Russia Investigation Was Illegitimate From The Start
The briefings were organized by the Justice Department and the Office of Director of National Intelligence. Sanders said no White House staffers - including Kelly - will be present at Thursday's meeting.