Spain's National Court, which deals with major corruption cases, added that Rosell's wife, an Andorran lawyer and three other people would also stand trial.
The 54-year-old is suspected of having siphoned off €15 million ($17.5 million) in illegal commissions from a TV rights deal for the Brazilian national team along with Ricardo Teixeira, the former head of the Brazilian Football Confederation.
Rosell had previously lived and worked in Brazil, where he forged many business links.
The contract was signed in 2006 to hand over the rights to 24 Brazil friendly matches to a company based in the Cayman Islands but tied to a Saudi group.
Altogether, Rosell and his wife received some €15 million in their accounts, of which €6.6 million went to them and the rest was destined for Teixeira.
Teixeira, a former FIFA vice-president, has been indicted by US Justice Department prosecutors investigating the Fifa corruption scandal.
Rosell is also suspected of having received some five million euros illicitly as part of Nike's sponsorship deal with the Brazilian team.
Rosell, his wife and the four others are accused of mounting a “criminal organisation”.
He resigned as Barcelona president in 2014 over the murky transfer dealings that brought Brazilian striker Neymar to the club from Santos.
He was later cleared of all charges in connection with an alleged tax fraud case over the transfer following an agreement with prosecutors.
Rosell is nevertheless being probed for fraud and corruption relating to a parallel complaint filed by Brazilian investment company DIS, which owned 40 percent of Neymar's sporting rights at the time of his transfer.
DIS claims it was cheated out of its real share because part of the transfer fee was concealed by Barcelona, Santos and the Neymar family.
Rosell can still appeal the judge's decision to send him to trial.