Poly(vinyl alcohol) (PVA) was found to form complexes with PbCl2, Pb(NO3)(2), and Pb(CH3COO)(2). Different complex compositions were prepared by casting technique. Microdomains were observed in the case of the PbCl2-PVA system. Complexes of PbCl2-PVA system are semicrystalline over the entire composition range. PbCl2-PVA complexes are stable to temperatures greater than 350 degrees C in comparison to 225 degrees C of pure PVA. The general features of the microdomains depends upon the temperature and the salt concentration. The hardness properties of the binary mixture were found to change in a nonlinear mode exhibiting a maximum value with the increase of the PbCl2 content and in a linear mode for the other salts.