The reaction between 6-methyl-4-phenylamino-pyran-2-one and aroyl chlorides with potassium selenocyanate in the presence of catalytic amounts of N-methylimidazole under solvent-free conditions provided a simple and efficient one-pot route for the synthesis of 2-aryl-7-methyl-1-phenyl-4-selenoxo-1,4-dihydro-pyrano[4,3-d]pyrimidin-5-one. This new protocol offers advantages such as mild reaction conditions, short reaction time, easy work-up, high yields of biological active products and does not involve any hazardous solvent.