A cholic acid-based bis-primary amine is capable of promoting the insertion of CO2 into epoxides with the cooperative aid of an iodide anion. This framework is transformed in situ into a bis-carbamic acid. The latter is the active catalytic species, operating through H-bonding interactions. Our system works with complete atom economy, under solvent-free, metal-free, and mild conditions. Also, it can be recycled.