Gen. Gustavo Ricaurt, the police chief in Cali, said Janer Copete Victoria, 38, faces charges of participating in kidnappings as well as the bombing last Sunday, the Latin American Herald-Tribune reported. Grenades and other weapons were seized during the arrest, Ricaurt said.
Two people were killed and 38 injured when the car bomb exploded. The attack was aimed at the building containing the intelligence archives of the metropolitan police.
Police shot and killed the driver of the car.
Investigators say Copete Victoria, using the alias "Manuel 48," is a member of the "Miller Perdomo" column of the Revolutionary Armed Forces of Colombia, known by its acronym FARC.
Police offered a reward of about $42,000 for information leading to arrests.