An environmentally benign approach for the synthesis of novel 7-substituted 5-aryl-1H-pyrimido[4,5-d]pyrimidine-2,4-diones, using mineral supports for their catalytic role and as energy transfer media, is described. The methodology eliminates the usage of solvent during the reaction. The rate enhancement and high yield is attributed to the coupling of solvent-free conditions with microwaves. Further, the role of various supports is studied during the reaction and it is concluded that a MW-assisted basic alumina catalysed reaction is the best in terms of catalysis as well as reaction time and yield.Key words: microwave (MW) irradiation, SBT, pyrimido[4,5-d]pyrimidines, alumina, environmentally benign.