The regional development and poverty alleviation program in contiguous destitute areas are concerning to the realization of the goal for building a well-off society in a comprehensive way. This paper analyzes the differences of county economic development of western areas in Hunan Province by using the statistic data from 2010, which is the typical case in contiguous destitute areas. This paper gives a comprehensive evaluation and rank of economic development of 39 counties and cities in western areas in Hunan Province by using principal component analysis method, as well as a hierarchical cluster analysis on economic development by using Ward＇ s method. The findings show that the county economic differences of western areas in Hunan Province is large, accordingly it can be divided into four levels in terms of economic development. Five counties like Shaodong County, Hecheng District and so on can be classified into the highest level, and nine counties like Dongkou County, Longhui County and so on are secondary to it, eleven counties like Zhongfang County, Zhijiang County and so on are in the middle level, fourteen counties like Jianghua County, Jiangyong County and so on are the worst.