An efficient and environmentally benign exclusive method of synthesis of 3-(amine dithiocarbamyl ) phthalides has been developed using reaction of 3-chlorophthalide with amine dithiocarbamate effectively in an aqueous medium with excellent yields under microwave irradiation. The results were compared with conventional methods. All the ecofriendly synthesized 3-(amine dithiocarbamyl) phthalides were characterized by analytical and spectral methods. The photochemical decomposition of 3-(amine dithiocarbamyl) phthalides yielded meso-3, 3’- dihydrobiphthalideas the onlyisolable product. The mechanisms of the green synthesis and photochemical reactions have also been studied.