Many people around the world rely on groundwater for drinking and sanitation, however, they are exposed to various health risks from the naturally occurring groundwater arsenic (As). Air-cathode Assisted Iron Electrocoagulation (ACAIE) using Carbon Black Pearls 2000® cathode was previously shown catalyse the removal of groundwater As by producing hydrogen peroxide (H2O2). This work explored Vulcan® XC-72, and Printex® L6 Carbon as alternative cathodes for iron electrocoagulation which are more selective towards the 2-electron oxygen reduction reaction into H2O2 compared to Carbon Black Pearls®. The cathodes were tested in an ACAIE set-up to treat synthetic groundwater spiked with 1,500 μg/L of As at different charge dosage rates (CDR) from 1.56 C/L-min to 100 C/L-min with a total charge dosage of 600 C/L for all set-ups. Although the electrocoagulation energies among the cathodes were similar, the use of Printex® cathode for ACAIE remediated the groundwater for all CDR with final As levels below 10 μg/L. This is in contrast with the less selective Carbon Black Pearls® at low CDR, and the less active Vulcan® Carbon at high CDR where the treated groundwater may still have As levels above 10 μg/L. Future research would explore modifications in the carbon materials and reactor configuration to further optimize ACAIE in removing groundwater As.