Taking Anhui Province as an example, quality evaluation system of eco-environment and urbanization level, which were composed of thirty-two indexes was constructed. A comprehensive assessment of the urbanization and the eco-environmental quality was completed by the method of principal component analysis. The marginal eco-environmental effect of the urbanization evolution was measured by using the STIRPAT(stochastic impacts by regression on population, affluence, and technology) model and partial least squares regression method. The results showed that:(1) Comprehensive appraisal index of the urbanization which presented fluctuating increment rose from 43.83 in 1996 to 83.83 in 2011;(2) The comprehensive appraisal index of eco-environment rose from 40.95 in 1996 to 80.95 in 2011, and it showed steady increasing state in general, indicating that the quality of eco-environment was better.(3) The urbanization evolution and the eco-environmental quality presented positive correlation, and the urbanization evolution showed weak positive effects on the eco-environment, the marginal elastic coefficient was 0.010 2.