Diniz took temporary charge of Brazil when Tite left the role following their quarter-final exit at the World Cup in Qatar and will be replaced by Real Madrid coach Carlo Ancelotti next year.
However, the 49-year-old coach, who splits his time with club side Fluminense, still hopes to make his mark with the national team and keep them top of the South American qualifying competition.
"(Neymar and Vinicius) are extremely good players, very intelligent, skilful and they like each other, there is also Rodrygo, a player of a very high level," he said.
"We hope they get on well in tomorrow's game, as they have done in training, and that they can have a great game."
Vinicius, who usually plays in the same position as Neymar, returns to the squad after missing the first two qualifiers through injury.
"My first interaction with Vinicius was excellent, today he is one of the greatest players in world football. Let's hope he is comfortable to play," he added.
Finding balance and building unity is Diniz's main objective in order to have a "competitive team".
"I feel a positive camaraderie from the players, who like each other very much, forming that feeling of family, the older ones know how to welcome very well those who arrive, both my committee and the players called up," he said.
Brazil host Venezuela in Cuiaba before facing Uruguay in Montevideo five days later.
