The effect of addition of gypsum on the rheology, physico-mechanical properties, thermal properties and morphology development of polymer composites based on polyvinyl chloride (PVC) and waste-gypsum with and without methylene-butadiene-styrene (MBS) has been studied. It was shown that the replacement of gypsum for methylene-butadiene-styrene (MBS) component in PVC/gypsum polymer composites enhanced the tensile strength and stiffness of composites, but gradually decreased its impact strength. The observation of morphology, the results of the physico-mechanical properties and thermal properties proved simultaneously that PVC/gypsum composite with the waste-gypsum content of 22.56 wt% reached the optimum results among five kinds of PVC/gypsum polymer composite materials investigated.