An electrostatically enhanced phenol is utilized as a straightforward, sustainable, and potent one-component organocatalyst for the atom-economic transformation of epoxides to oxazolidinones under microwave irradiation. Integrating a positively charged center into phenols over a modular one-step preparation gives rise to a bifunctional system with improved acidity and activity, competent in rapid assembly of epoxides and isocyanates under microwave irradiation in a short reaction time (20-60 min). A careful assessment of the efficacy of various positively charged phenols and anilines and the impact of several factors, such as catalyst loading, temperature, and the kind of nucleophile, on catalytic reactivity were examined. Under neat conditions, this one-component catalytic platform was exploited to prepare more than 40 examples of oxazolidinones from a variety of aryl- and alkyl-substituted epoxides and isocyanates within minutes, where up to 96% yield and high degree of selectivity were attained. DFT calculations to achieve reaction barriers for different catalytic routes were conducted to provide mechanistic understanding and corroborated the experimental findings in which concurrent epoxide ring-opening and isocyanate incorporation were proposed.