The effect of blending various methacrylate copolymers on the physical and mechanical properties of poly(vinyl chloride) (PVC) has been investigated. Copolymers of methylmethacrylate with methylacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate in 80:20 and 50:50 wit methylmethacrylate have been prepared and characterized by nuclear magnetic resonance spectroscopy. Polyblends of PVC and such polyacrylates have been prepared in 80:20 ratio by melt blending technique and characterized by thermomechanical analysis to study the glass transition behavior vis-à-vis the compatibility of these blends. Mechanical properties of these blends revealed a substantial increase in impact strength particularly when long chain acrylate polymers like butyl acrylate and 2-ethyl hexyl acrylates are used; however, there is a decrease in the yield stress and initial modulus. A shift from brittle failure to ductility has been observed in blends of PVC on incorporation of these acrylate copolymers. Scanning electron microscopic studies have been carried out to support these observations.