In this present study, a novel environment-friendly and bio-polymeric hybrid ultrafiltration membrane was fabricated by incorporating poly(methyl vinyl ether maleic anhydride) (PMVEAMA) into the poly(lactic acid) (PLA) polymer matrix. The integration of PMVEAMA into PLA significantly altered the membrane's structural morphology, functional characteristics, and filtration performance. As a result, key functional parameters like membrane porosity increased from 14.34% to 33.09% with the water content enhanced from 25.42% to 42.33%. Furthermore, the MWCO of the membrane reached up to a maximum of 20kDa with an average pore size of 4.16nm, subsequently improving the flux of the membrane from an initial value of 108.47 Lm-2h-1 to 260.35 Lm-2h-1. This functional capacity of the synthesized membrane was further assessed by testing its ability to filter toxic chlorophenolic compounds. Rejection and permeation studies reveal 44.64% pentachlorophenol (PCP) and 51.85% 2,4-dichlorophenol (DCP) rejection with solute permeation flux of 121.5 Lm-2h-1 and 134.51 Lm-2h-1, respectively. Moreover, fouling studies revealed enhanced PCP and DCP flux recovery ratios of 50.94% and 51.40%, respectively, with a significant reduction in the flux decline rate. Additionally, the synthesized PLA/PMVEAMA membranes improved stability and regenerative properties up to 12 filtration cycles and antifouling properties highlight its potential to filter chlorophenolic compounds from wastewater.