Abstract A novel and efficient approach for the regioselective selenylation of 4 H ‐pyrido‐[1,2‐ a ]‐pyrimidin‐4‐ones with diselenides at room temperature has been developed. This procedure is catalyzed by N ‐iodosuccinimide under metal‐free conditions with a broad range of substrate scopes and affords C3 selenylation products in good to excellent yields. Furthermore, the sulfenylation with diphenyl disulfides and 4‐methylbenzenethiol in this transformation is successful.