Martinez has been linked with a move to the Camp Nou in recent weeks as Barcelona aim to secure a long-term replacement for the ageing Luis Suarez.
The 22-year-old Argentine is enjoying his best run of form at the San Siro since moving to Italy last season, with 16 goals across all competitions for Antonio Conte’s men.
Neymar previously enjoyed a four-year spell at Barcelona, forming a lethal attacking partnership with Lionel Messi and Luis Suarez before departing controversially for Paris Saint Germain in a world record deal three years ago.
The 28-year-old Brazilian tried and ultimately failed to engineer a return to Barcelona last season but senior figures at the club are still interested in bringing him back.
Rivaldo, who won two La Liga titles with Barcelona, believes Neymar is the best option for the Blaugrana currently as he is ready-made.
"The rumours are growing about Barcelona's intention to sign Neymar and Lautaro Martinez in the next transfer window," the 2002 FIFA World Cup winner wrote in his column for Betfair.
"Although the young Argentinian is a good player, I think that only Neymar is a certain bet to claim a place in the starting XI side by side with Messi.
"Looking at the last few years we have seen many valuable players who didn't manage to play alongside Messi - failing to perform under the expectations.
"But Neymar - like Luis Suarez - is one of the few players in the world that doesn't feel pressure on the pitch, always playing with plenty of personality.
"He never gets frightened and it would be a safe option for the club while Martinez is a young, talented forward that perhaps in two or three years may become a good signing.
"For now I think the club should prioritise Neymar. I'm a fan of his qualities and personality and I know that sometimes I'm liable to criticism as some Barcelona fans didn't like the way Neymar decided to leave the club.
"But the truth is that he is a different player now who should be a nice help to Messi and co. in trying to win another Champions League."
