2-Phenyl-substituted 1,3-benzodioxole derivatives were synthesized by microwave irradiation by reacting catechol with benzoic acid derivatives in the presence of polyphosphoric acid as a catalyst which acts as a solvent and also as a cyclizing agent. This synthesis has various advantages over other catalytic conventional synthesis because it saves time, increases yield, and is a simple, economical, and effective synthesis. Moreover, this is also an excellent green chemistry approach as it does not require additional toxic solvents or harmful chemicals, and overall it reduced energy utilization than the other methods of synthesis.