The pair were killed instantly after losing control of the Fiat Punto they were travelling in on a bend and smashing into a tree.
The accident happened around 8am local time on Saturday on the main road between the towns of Pujato and Casilda in the Argentinian province of Santa Fe.
Barcelona FC said in a tweet as news of the tragedy involving its ex 28-year-old player emerged: “We are dismayed by the death of Maxi Rolon, a Barcelona youth football player from 2010 to 2106.
“We express our deepest condolences and send full support to his family. Rest in peace.”
The Argentine Football Association said: “We deeply regret the loss of the young footballer Maximiliano Rolon, who played for national youth teams and was under-20 South American champion in 2015.”
Pele’s lifelong club Santos, where Rolon spent a year, also expressed their dismay in a tweet, saying: “Our condolences to all his family and friends. Rest in peace Maxi.”
Both men were playing football for teams in the town of Chabas near to where the crash happened.
They were on their way to pick up a relative in Rosario, the city where former Barcelona star Lionel Messi was born and grew up, when their car came off the road.
No other vehicles were involved but a routine investigation into the accident is ongoing.
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Rosario-born Rolon started his youth career with local club Atletico Lujan before joining Barcelona’s youth setup in 2007.
He moved to La Masia, the Catalan giant’s famous youth academy which has produced world class players including Messi, Xavi and Andres Iniesta, three years later.
He made his debut as a professional in October 2014 and scored his first senior goal for Barcelona’s reserves in September the following year.
Rolon left Barcelona for Brazilian side Santos in February 2016 and returned to Spain at the start of the following year for a short-lived experience with second-tier side CD Lugo.
As well as representing Argentina at the South American Youth Football Championship in Uruguay in 2015 along with another brother Leonardo, Maxi was also included in the squad for the 2015 FIFA U-20 World Cup in New Zealand.