The interactions between microplastic-derived dissolved organic matter (MPs-DOM) and heavy metals (Cu, Pb, and Cd) regulate the complex environmental transport behavior of pollutants in terrestrial and aquatic environments. In this study, fluorescence excited emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC) and electrospray ionization coupled Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) were employed to investigate the complexation mechanism of MPs-DOM with heavy metals, as well as the effects of different environmental occurrences of MPs-DOM on the transport behaviors of heavy metals in saturated porous medium. The findings demonstrated that MPs-DOM, particularly humic-like substances containing aromatic structures and various oxygen functional groups, could form stable complexes with heavy metals. This interaction significantly altered the transport capacity of Pb and Cu in saturated porous media. It is noteworthy that MPs-DOM in the free and deposited states in the environment may have markedly disparate effects on heavy metal transport. MPs-DOM in the free state may facilitate the co-migration of heavy metal ions in porous media, thereby enhancing the mobility of heavy metals. In contrast, sedimentary-state MPs-DOM can retain heavy metals in porous media and inhibit their migration through complexation with them.