Microplastics (MPs) have become a global concern as they can accumulate pollutants in aquatic environments. In this research, Cu(II) and non-degradable (polyamide, PA), degradable (polylactic acid, PLA) MPs were employed to reveal the potential connection among different aged MPs and heavy metal pollutants. The aging processes of MPs induced alterations in the surface morphologies, led to an augmentation of the specific surface area, and formed more biofilm and oxygen-containing groups on the MPs surface. The Qe of PA and PLA MPs increased from 0.102 and 0.989 to 1.192 and 2.457 mg/g after aging, respectively. The analysis of site energy distribution further verified that the enhanced adsorption capacity resulted from more high-energy adsorption sites obtained during the aging processes of MPs. Moreover, pathogenic bacteria and resistant bacteria were accumulated on the surface of MPs regardless of the aging environment, and the abundance and diversity of pathogenic bacteria on the biofilm of the PA surface were greater than those on the PLA MPs. This research offers an insight into the mechanism underlying microbial colonization and adsorption in the relationship between MPs and Cu(II), which is beneficial for judging the enrichment of heavy metals on MPs within the aquatic environment.