Microplastic particles are persistent micropollutants that provide a substrate for the growth of bacterial biofilms, posing a threat to the environment. This study explores the changes in commercially available food containers made of conventional (polypropylene PP, polyethylene terephthalate PET), innovative biodegradable (Mater-Bi) and natural (wood and cellulose) materials, when introduced in the surface waters of Lake Maggiore for 43 days. Spectral changes revealed by FT-IR spectroscopy in PET and Mater-Bi, and changes in thermal properties of all human-made material tested indicated a degradation process occurred during environmental exposure. Despite similar bacterial richness, biofilms on PET, PP, and Mater-Bi differed from natural material biofilms and the planktonic community. Human-made material communities showed a higher proportion of potential pathogens, with PET and PP also exhibiting increased abundances of antibiotic resistance genes. Overall, these findings stress the need for dedicated strategies to curb the spread of human-made polymers in freshwaters, including innovative materials that, due to their biodegradable properties, might be perceived less hazardous for the environment.