Anaerobic digestion provides a solution for the treatment of vegetable waste water (VWW), but there are currently limited targeted treatment methods available. Building upon previous studies, this research investigated the effects of polyacrylamide-modified magnetic micro-particles (MMP) on anaerobic digestion (AD) of VWW. Three variations of these particles were created by grafting anionic, cationic, and non-ionic polyacrylamide (PAM) onto the MMPs’ surfaces, resulting in aPAM-MMP, cPAM-MMP, and nPAM-MMP, respectively. In AD experiments, the addition of aPAM-MMP notably enhanced the degradation of chemical oxygen demand (COD) in VWW. COD decreased to 1290 mg/L in the reactor with aPAM-MMP by day 12 and remained low, while the other reactors had COD concentrations of 4137.5, 5510, and 3010 mg/L on the same day, decreasing thereafter. This modification also improved the production and utilization of hydrogen gas and volatile fatty acids (VFAs), along with the conversion of methane. When tested for bioaffinity using fluorescent GFP-E.coli bacteria, the aPAM-MMP, cPAM-MMP, and nPAM-MMP demonstrated increases in fluorescence intensity by 51.66%, 36.13%, and 37.02%, respectively, compared to unmodified MMP when attached with GFP-E.coli. Further analyses of microbial community revealed that the reactor with aPAM-MMP had the highest microbial richness and enriched bacteria capable of organic matter degradation, such as Bacteroidota, Synergistota, Chloroflexi, Halobacterota phyla, and Parabacteroides, Muribaculaceae, and Azotobacter genera. In conclusion, our experiment verifies that APAM-MMP promotes anaerobic treatment of VWW and provides a novel reference point for enhancing VWW degradation.