Inspired by biomimetic oxybromination, a binary catalyst system composed of sodium phosphotungstate and n-Bu₄NBr (TBAB) was developed for facile synthesis of styrene carbonate in a single operation from styrene and CO₂ using 30% H₂O₂ as an oxidant. Notably, the presence of a base like NaHCO₃ markedly improved the formation of styrene carbonate. Interestingly, an oxidized product, i.e.phenacyl benzoate, could be obtained exclusively in good yield directly from styrene in the absence of CO₂ under the appropriate reaction conditions.