The reactions of 5-azido-4-alkoxycarbonyl-1,2,3-triazoles with active methylene nitriles (phenylacetonitrile, malononitrile) yield bis-[1,2,3] triazolo [1,5-a:4′,5′-d] pyrimidinones 7 instead of the previously reported3 bis[1,2,3] triazolo[1,5-a:4′,5′-e] pyrimidinones 6. The structures were established by 1H and 13C NMR analyses and confirmed by a crystal structure determination of a selected derivative obtained by methylation.