A new, efficient and mild approach for the oxidative dehydrogenation of dihydropyrimidinones and thiocyanation of aromatic compounds using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane (THPDPE) as a terminal oxidant was developed. Initially, various substrates bearing different electron-donating and electron-releasing functionalities were synthesized, and next under the optimized reaction conditions the desired products were yielded after an easy work-up. All of the reactions proceeded in short reaction times, and 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane (THPDPE) proved its potential to yield the desired products in high yields.