In the present study, we are reporting a simple and efficient method for the one‐pot synthesis of the biologically important heterocyclic molecules 5‐unsubstituted 3,4‐dihydropyrimidin‐2‐ones and thiones using gem‐dibromomethylarenes, oxalacetic acid, and urea or thiourea. Gem‐dibromomethylarenes are used as aldehyde equivalent for the efficient synthesis of 3,4‐dihydropyrimidin‐2‐ones/thiones. This reaction offers advantages for the synthesis of these compounds, including ready availability of the starting materials, experimental simplicity and in good yields. Besides, the synthesized molecules are interesting for their biological and pharmacological actions.