Poly(vinyl chloride) (PVC)‐based nanocomposites containing 2 wt% zinc oxide (ZnO) nanoparticles were prepared by solution casting and the effect of the PVC molecular weight (MW) on the morphology, thermal properties, and thermogravimetric behavior was studied. The addition of ZnO nanoparticles to PVCs of different MWs increased the glass transition temperature (Tg) of the resulting nanocomposites, the extent of which was dependent upon the MW of the PVC matrix. The nanocomposite samples exhibited broadened transition zones as compared with their unfilled PVC matrices. The extent of transition zone broadening was also controlled by the MW of the PVC matrix in the nanocomposites. In the absence of ZnO nanoparticles, the increase in MW of PVC had no effect on the breadth of the transition zone. The TGA results showed that the incorporation of ZnO nanoparticles into PVC matrices of different MWs accelerated the first stage weight loss via the nanoparticle catalytic effect through removal of HCL from the polymeric chains. The presence of ZnO nanoparticles lowered the second stage weight loss, and the char yield obtained for nanocomposites samples was significantly greater than that obtained for neat PVC samples. At low MWs, the presence of ZnO nanoparticles had no effect on the first stage of thermal degradation process. The presence of ZnO nanoparticles in the matrix in different nanocomposites was revealed by SEM observations, and the EDX analysis demonstrated a progressive improvement in the distribution and dispersion state of ZnO nanoparticles in the PVC‐based nanocomposites as the MW of PVC matrix gradually increased. J. VINYL ADDIT. TECHNOL., 25:E63–E71, 2019. © 2018 Society of Plastics Engineers