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Microplastics (MPs) are prevalent emerging pollutants in soil environments, acting as carriers for other contaminants and facilitating combined pollution along with toxic metals like cadmium (Cd). This interaction increases toxic effects and poses substantial threats to ecosystems and human health. The objective of this study was to investigate the hydrodynamic adsorption of Cd by conducting experiments where polystyrene microplastics (PS) and biochar (BC) coexisted across various particle sizes (10 µm, 20 µm, and 30 µm). Then, soil incubation experiments were set up under conditions of combined pollution, involving various concentrations (0.5 g·kg−1, 5 g·kg−1, 50 g·kg−1) and particle sizes of PS and BC to assess their synergistic effects on the soil environment. The results suggest that the pseudo-second-order kinetic model (R2 = 0.8642) provides a better description of the adsorption dynamics of Cd by PS and BC compared to the pseudo-first-order kinetic model (R2 = 0.7711), with an adsorption saturation time of 400 min. The Cd adsorption process in the presence of PS and BC is more accurately modeled using the Freundlich isotherm (R2 > 0.98), indicating the predominance of multilayer physical adsorption. The coexistence of 10 µm and 20 µm PS particles with BC enhanced Cd absorption, while 30 µm PS particles had an inhibitory effect. In soil incubation experiments, variations in PS particle size increased the exchangeable Cd speciation by 99.52% and decreased the residual speciation by 18.59%. The addition of microplastics notably impacted the exchangeable Cd speciation (p < 0.05), with smaller PS particles leading to more significant increases in the exchangeable content—showing respective increments of 45.90%, 106.96%, and 145.69%. This study contributes to a deeper understanding of the mitigation mechanisms of biochar in the face of combined pollution from microplastics and heavy metals, offering theoretical support and valuable insights for managing such contamination scenarios.