A series of novel 4‐hetaryl substituted pyrazolo[1,5‐ a ][1,3,5]triazines were synthesized by microwave assisted reaction between O,S ‐diethyl hetaroylimidothiocarbonates and 5‐amino‐3‐aryl‐1 H ‐pyrazoles under solvent‐free conditions. This procedure led to the formation of mixtures of two new pyrazolotriazine derivatives in a 1:4 ratio, which were separated by column chromatography being their corresponding structures unambiguously established by spectroscopic and analytical techniques. Comparison of the reactions mediated by microwave irradiation and by conventional heating in solution of DMF showed that both procedures afforded the same mixtures of products, but the first approach required shorter reaction times and gave higher yields than the second one.