A fast and efficient method for the synthesis of naphthopyranopyrimidinones derivatives in excellent yields was developed through cyclocondensation reaction between previously prepared pyrimidinic hydrazides and some electrophilic species such as 2,4-pentanedione, 2,5-hexanedione, cyclic anhydrides, and phenylthioisocyanate under microwave irradiation. Compared to the conventional methods applied, it was found that better yields and shorter reaction times were achieved using microwave-assisted synthesis. Structures of all synthesized compounds were established on the basis of spectroscopic methods including H-1 NMR, C-13 NMR, and HRMS-ES.