Most microplastics and arsenic (As) have been released into farmland via industrial and agricultural activities, posing a potential threat to crop growth and food safety. Thus far, few studies have focused on the phytoxicity of microplastics and As to leafy vegetable. In this study, we evaluated the single and combined toxicological effects of polymethyl methacrylate (PMMA) and As(V) on rapeseed (Brassia campestris L.). Single treatments of two sizes of PMMA particles, namely PMMA nano-plastics (PMMANPs) and PMMA micro-plastics (PMMAMPs) and As(V) significantly (P < 0.05) inhibited the germination index (GI) of rapeseed. The IC50 indicates that PMMANPs were more toxic than PMMAMPs. Combine-pollution experiments demonstrated that the GI, biomass, root length, and sprout length of the rapeseed under the combined treatment were lower than those subjected to As(V) or PMMANPs single treatment. Analysis of variance showed that the interaction effects of PMMANPs and As(V) for GI and root length were significant, and there was synergistic interaction between PMMANPs and As(V) on rapeseed germination. PMMANPs promoted the accumulation of As in sprouts under high As(V) concentrations (40 and 60 mg/L). The activities of lipase in rapeseed generally increased under single and combined treatments of As(V) and PMMANPs, and while α-amylase activities first increased and then decreased with the increase of PMMANPs. It appears that the combined stress of microplastics and As(V) exhibited synergistic interaction on the growth of rapeseed.