An electrostatically enhanced phenol as a simple and competent bifunctional organocatalyst for the atom‐economical conversion of epoxides to cyclic carbonates under environmentally benign conditions is described. Incorporating a positively charged center into phenols through a modular one‐step synthesis results in a bifunctional system with enhanced acidity and reactivity, capable of epoxide activation, a halide nucleophilic ring‐opening process, and CO2 incorporation in a synergistic fashion. A rational survey of the efficiency of different positively charged phenols and the influence of different parameters, such as temperature, catalyst loading, and the nature of the nucleophile, on catalytic activity was conducted. In addition, the time‐dependent conversion of epoxide into the corresponding cyclic carbonate was further explored by FTIR‐ATR and 1H NMR spectroscopy. This bifunctional catalytic platform is among one of the mildest and most efficient metal‐free systems that is capable of converting a variety of epoxides into cyclic carbonates under virtually ambient conditions. The 1H NMR titration experiment validated the bifunctional catalytic mechanism wherein both the epoxide activation and the nucleophilic ring‐opening process occur in concert en route to carbon dioxide fixation.