Co-impregnated Sb2O3–CuO–NaCl/SiO2 catalysts were investigated for the direct gas-phase synthesis of propylene oxide (PO) from propylene and molecular oxygen at atmospheric pressure. The trimetallic system was optimized for PO formation by varying the Sb:Cu:Na ratios, total metal loadings and calcination temperatures. At a reaction temperature of 250°C and propylene/oxygen molar ratio=1:4, the highest performing catalyst achieved 40–45% PO selectivity with 0.4–0.7% propylene conversion without a co-feeding gas. The coexistence of Sb2O3 and CuO crystals was determined to play a vital role in propylene epoxidation, while NaCl helped to suppress combustion.