Density functional theory (DFT) calculations are carried out for polyvinyls repeating units at the 3LYP/6-31 G(d) level, and the calculated results of E-T, E-int, C-V, S, Q(ii), mu, alpha and q(-) are used to predict V (298 K), P-s, F-d, R-LL, chi, H-vsum, U-R and U-H. Multiple linear stepwise regression analysis is used to generate eight more physically meaningful quantitative structure-property relationship (QSPR) models having correlation coefficient R of 0.996 for V (298 K), 0.998 for P-s, 0.997 for F-d, 0.997 for R-LL, 0.997 for X, 0.992 for H-S, 0.992 for U-R and 0.991 for UH, and the conclusions are in consistence with theoretical analysis. Investigated results indicate QSPR models given here are easy to apply and have good predictive capability. (c) 2005 Elsevier Ltd. All fights reserved.