This paper decomposes and compares deviating rate of industrial structure to make empirical analysis of the employment of the tertiary industry of Yunnan Province, holds that there is great employment potential in the tertiary industry of Yunnan Province and points out the selection of inner industries of the tertiary industry for effective growth of the employment. The research results show that, in recent ten years, the employment contribution rate of the primary, secondary and tertiary industry of Yunnan Province is 27.8 percent, 2.2 percent and 69.9 percent respectively, 69.9 percent of new employment is provided by the tertiary industry, when the tertiary industry output value increases 1 percent, 15.6 thousand new employees are averagely employed and the employment of the tertiary industry is 9 thousand more than that of the secondary industry, that the employment capability of the tertiary industry is not sufficiently embodied when the tertiary industry of Yunnan develops and there is a lot of employment space and that the main industries of the tertiary industry for Yunnan to enlarge employment are wholesale, retail, trade, food and beverage industry but employment space is difficult to be enlarged in traffic, transportation, storage, post and communications industry.