Abstract Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T 1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.