An aminopyridinium ionic liquid is presented as a green, tunable, and active metal‐free one‐component catalytic system for the atom‐efficient transformation of oxiranes and CO2 to cyclic carbonates. Inclusion of a positively charged moiety into aminopyridines, through a simple single‐step synthesis, provides a one‐component ionic liquid catalytic system with superior activity; effective in ring opening of epoxide, CO2 inclusion, and stabilization of oxoanionic intermediates. An efficiency assessment of a variety of positively charged aminopyridines was pursued, and the impact of temperature, catalyst loading, and the kind of nucleophile on the catalytic performance was also investigated. Under solvent‐free conditions, this bifunctional organocatalytic system was used for the preparation of 18 examples of cyclic carbonates from a broad range of alkyl‐ and aryl‐substituted oxiranes and CO2, where up to 98 % yield and high selectivity were achieved. DFT calculations validated a mechanism in which nucleophilic ring‐opening and CO2 inclusion occur simultaneously towards cyclic carbonate formation.