Although recent studies have been conducted on the pollution and toxicity of microplastics with heavy metals or antibiotics, it is necessary to further investigate the coexistence of antibiotics and heavy metals on the surface of microplastics. In this study, the mechanisms of As(III) adsorption by polystyrene (PS) and polyamide (PA) microplastics in the presence of antibiotics (ciprofloxacin, CIP) were investigated. Adsorption behavior was investigated using kinetic and isotherm models, and the effects of microplastic particle size, aging, ion concentration, pH, xanthic acid (FA), and tannic acid (TA) were considered. Adsorption kinetics and isotherm models showed that the kinetics of As(III) adsorption on PS were consistent with a pseudo-first-order model; the kinetics of adsorption on PA were more consistent with segmented linear regression. The Freundlich model is consistent with the adsorption isotherms of As(III) on PS and PA. The smaller the microplastic particle size and the longer the aging time, the better the adsorption of As(III). Increasing NO3−significantly inhibited the adsorption of As(III) by PS, while it first promoted and then inhibited the adsorption by PA. The effect of pH was similar to that ofNO3−. The adsorption of As(III) by PS was significantly promoted by FA and TA, regardless of the presence of CIP; the adsorption of As(III) by PA was inhibited. Scanning electron microscopy (SEM) was used to characterize microscopic morphology of pristine and aged PS and PA microplastics; Fourier transform infrared (FTIR) and X-ray absorption spectroscopy (XPS) revealed changes in surface functional groups of PS and PA, while demonstrating the importance of different functional groups in exogenous additives (CIP and dissolved organic matter, DOM) in the adsorption of As(III). This study provides new insight into adsorption behaviors and interaction mechanisms between ternary pollutants.