Electrochemical synthesis of some new sulfonamide and disulfonamide derivatives was carried out via the air-assisted electrochemical oxidation of phenylhydrazine (PHD) and 4-hydrazineylbenzenesulfonamide (HBS) derivatives in the presence of arylsulfinic acids (AS1-AS3), respectively. The results indicated that electrochemically generated phenyldiazene (PDZ) participated in Michael type reaction with arylsulfinic acids and were converted to the corresponding sulfonamide derivatives. Here we describe the preparation of some new sulfonamide derivatives (P1-P5) in high yields in aqueous/ethanol mixture, under constant current conditions, without toxic reagents at a carbon electrode using an environmentally friendly method. Also, antibacterial tests indicated that the products showed good antibacterial performance against both gram-positive and gram-negative bacteria.