An off-office auditing assessment system of cadres on natural resources and environmental responsibility is established based on the PSR model in this paper, considering the practices of preparing natural resources balance sheet. This system can make a comprehensive evaluation on performance of cadres and reveal the relationship between the indexes by a motivation analysis between the final evaluation results and each index. Based on this assessment system, an empirical analysis of the natural resources and environmental conditions of China’s 31 provinces（autonomous administrative region, municipalities）in 2004, 2008 and 2012 respectively is conducted in this paper, using the principal component analysis method. In addition, a quantitative evaluation is made on the performance of leading cadres on natural resources assets and environmental responsibility in different provinces，districts and cities.