Hybrid blends of poly(amidoamine) PAMAM dendrimers with two Linear high polymers, poly(vinyl chloride), PVC, and poly( vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonance (NMR) spectroscopy, and tensile property measurements. The data suggest a much higher degree of interaction between components of PVAc-containing blends compared to those containing PVC.