Esteban Chaves' second-place finish at the Giro d'Italia sealed a place for the Orica-GreenEdge rider while Rigoberto Urán, the silver medalist from the 2012 London Games, has also been named in the squad.
"We chose these riders based on their careers, form, and experience - in the case of Rigoberto Urán and Sergio Henao - at past Olympics," said national coach Carlos Jaramillo.
"Miguel López is in there because he's a rider with a great future who has proven himself in big races. Also, it's a course for climbers and he could lend us a very good hand in that respect."
Jaramillo travelled out to Brazil to recon the road race route earlier this month, accompanied by Urán.
"It's a really tough course, made for climbers," he concluded. "It's one of the most difficult circuits I'm seen and whoever wins will be a true Olympic king."
Quintana, currently racing the Route de Sud, is aiming to win the Tour de France this July on his third appearance before targeting the Olympic road race on August 6. It will be his first appearance at the Olympic Games on what is regarded to be a climbing friendly 256.4km course starting and finishing at Fort Copacabana.
Ana Cristina Sanabria is the sole female representative for Colombia.