An efficient synthetic method for 3,6-epoxy[1,5]dioxocines via the condensation of salicyl aldehydes and epichlorohydrin, using benzyl triethylammonium chloride as catalyst, is described. The use of neutral or electron-deficient salicyl aldehydes in all cases was found to give 3,6-epoxy[1,5]dioxocine derivatives in good yields. The structural features were resolved by IR, NMR spectroscopy, mass spectrometry, and ultimately proved by X-ray crystallographic analysis.