Polystyrene (PS) and polyethylene terephthalate (PET) are commonly used materials that degrade into microplastics in the environment. These microplastics, possessing unique physical properties, can adsorb pollutants and contribute to composite pollution effects. This study examined the loading characteristics and toxic effects of PS and PET on six arsenic compounds, revealing that PS and PET displayed different adsorption capacities for these compounds, with PS demonstrating high adsorption for monomethylarsonic acid (MMA). The adsorption kinetics and isotherm analyses indicated that arsenic compounds quickly reached equilibrium on PS and PET. The kinetics were effectively described by pseudo-first-order models, and the isotherms aligned with the Langmuir and Freundlich models. Furthermore, simulated gastric fluid (SGF) and simulated intestinal fluid (SIF) were used to desorb arsenic compounds bound to PS and PET. The effects of aging, pH, salinity, anions, and humic acid (HA) on the ability of inorganic arsenic (iAs) to bind to PS and PET were analyzed. The results indicated that aging and HA increased the adsorption capacity of the microplastics, while salinity, anions, and elevated pH negatively affected this capacity. Additionally, the influence of microplastics and iAs on the clearance of free radicals by reduced glutathione (GSH) was explored. Microplastics inhibited the clearance of 1,1-diphenyl-2-picryl-hydrazyl (DPPH) by GSH, whereas iAs, especially arsenate, facilitated this process, likely due to synergistic effects with the oxidized form of GSH generated through GSH reactions. This study offers a theoretical foundation for understanding how microplastics transport various forms of arsenic compounds and their potential environmental risks.