In the presence of 1, 3-dimethylimidazolium iodide (1), 6-chloro-9-phenyl-9H-purine (7) and 4-chloro-5, 6-dimethylpyrrolo[2, 3-d]pyrimidines 40-42 undrwent uncleophilic aroylation with arenecarbaldehydes (5) to give the corresponding fused aroylpyrimidines 8 and 43-45. 1, 3-Dimethylbenzimidazolium iodide (2) was an effective catalyst for the similar synthesis of 7-aroyl-3-phenyl-3H-1, 2, 3-triazolo[4, 5-d]pyrimidines 16-21. In the synthesis of 4-aroyl-1H-pyrazolo[3, 4-d]pyrimidines 26-32, both azolium salts 1 and 2 were effective as catalysts. Moreover, 4-aroyl-7H-pyrrolo[2, 3-d]pyrimidines 43-45 were obtained in good yields via the 4-tosyl derivatives, in the presence of catalytic amounts of sodium p-toluenesulfinate (46) and the imidazolium salt 1. This catalytic aroylation was found to be a facile and useful method for the synthesis of 6-aroyl-9H-purines and their analogues.