Vulcanized acrylonitrile-butadiene rubber (NBR)/poly (vinyl chloride) (PVC) blends are mainly served as insulation rubber-plastic materials. However, methods to reuse the waste NBR/PVC composites lack research. Here, we found that the mechanochemically modified waste NBR/PVC composites powders (WNPP) could be an alternative to fresh NBR. According to the results, the optimal replacement amount of WNPP for NBR was 20%, and the highest feasible proportion was 40%. WNPP treated by solid-state shear milling technology (S3M) would have a high degree of desulfurization, and the cross-linked chains within WNPP would be transformed into free chains. While co-vulcanizing, the sulfur agents and heat would induce the free chains of WNPP to react with the polymer chains of the NBR substrate, thereby generating dangling chains to form a robust interfacial layer. It was beneficial for the improvement of the mechanical properties of reclaimed products. And the strain of the excellent recycled sample (20C) reached 707%. Moreover, the modified WNPP in the co-vulcanized rubber represented heterogeneity because of the internal residual crosslinked network and the not-melting PVC plastic phase. Although the heterogeneity of WNPP damaged the continuity of the NBR matrix, it also brought a better hysteresis loss capability to the composite. In conclusion, this work expanded the mechanochemical application scope in recycling NBR/PVC wastes.