Heavy metal-organic pollutants compound pollution at industrial legacy sites and have caused damage to the ecological environment and human health during recent decades. In view of the difficulty and high cost of post-contamination remediation, it is worth studying, and practically applying, cutoff walls to reduce the spread of pollution in advance. In this study, field-scale studies were carried out at e-waste dismantling legacy sites in Taizhou, Zhejiang Province of China, through the process of site investigation, numerical simulation, and cutoff wall practical application. Firstly, the concentrations and spatial distributions of Pb, Cd and polychlorinated biphenyls (PCBs) and poly brominated diphenyl ethers (PBDEs) were identified in both soil and groundwater. Then, potential dispersal routes of key combined contaminants (Pb and PCBs) at the soil-groundwater interface were systematically studied through numerical simulation applying Visual MODFLOW-MT3DMS. One site was chosen to predict the barrier effect of differently sized cutoff walls based on the migration path of compound pollutants. A protocol for a cutoff wall (50 m length × 2 m width × 3 m height) was finally verified and applied at the real contaminated site for the blocking of compound pollutant diffusion. Further, the groundwater quality of the contaminated site was monitored consecutively for six months to ensure the durability and stability of barrier measures. All pollutant indicators, including for Pb and PCB complex pollutants, were reduced to below the national Grade IV groundwater standard value, achieving environmental standards at these polluted sites and providing possibilities for land reuse. In summary, this field-scale test provided new ideas for designing cutoff walls to block the diffusion of complex pollutants; it also laid a basis for the practical application of cutoff walls in pollution prevention and control of complex contaminated sites and for soil-groundwater environmental protection at industrial heritage sites.