Rapid development of diffusion dialysis based on anion exchange membranes (AEMs) established its prominent significance as a leading candidate in the field of separation science and technology. AEM-based diffusion dialysis (DD) processes intended to acid recovery have generated much interest due to their exclusive selectivity. Here, we report the effects of novel Poly(DMAEM-co-gamma-MPS)-based AEMs for DD applications (acid recovery). Free radical polymerization was successfully done with the initiator azobisisobutyronitrile (AIBN) to achieve the desired polymer Poly(DMAEM-co-gamma-MPS). Finally, quaternization with EPTAC and methyl iodide was done to make the membrane matrix charged. The dosage of Poly(DMAEM-co-gamma-MPS) inside membrane matrix plays a crucial role to determine the physiochemical and electrochemical properties of the prepared membranes. The influence of Poly(DMAEM-co-gamma-MPS) on the acid recovery behavior of the membranes was explored in detail. The prepared membranes displayed high thermo-mechanical stability. At 25 degrees C, the acid dialysis coefficient (U-H) values were between 0.016-0.029 m/h, while the separation factors (S) ranged from 23.3 to 87.7. Both the acid recovery (7.25 times) and separation factors (similar to 3.6 times) are much higher than the commercial fiber supported anion exchange membrane DF-120B (U-H and S=0.004 m/h and 24.3, respectively). Prepared AEMs are the potent candidate for acid recovery via diffusion dialysis. The highlight of this work is the fabrication of new AEMs, which shows high acid dialysis performance and selectivity.