A number of Y-type push-pull compounds based on the [1,2,4]triazolo[1,5-a]pyrimidine core, namely 5,7- di(het)aryl-substituted 2-phenyl-[1,2,4]triazolo[1,5-a]pyrimidines, were obtained by transition metal free nucleophilic C-H functionalization. Substituents at both the C-5 and C-7 positions were introduced by successive treatment of the starting 6-bromo-2-phenyl-[1,2,4]triazolo[1,5-a]pyrimidine with Grignard reagents. In addition, the optical and electrochemical properties of the synthesized push-pull systems were studied.