This article uses the 569 farmer’s sampled data of seven villages in Shibing County of Guizhou Province to analyze the factors which affect the non-agricultural employment of the rural labor force through the Logit regression model. Study result indicates that the influencing factors include age, gender, family scale, the numbers of outdoor workers and so on, among which, the effect of age on non-agricultural employment is positive firstly and then negatively correlated, male, family scale and the employment relation with outside are positively correlated while the effect of marriage situation, per capita farming area, the aged, the children, the educated degree, whether having village cadre and so on is not obvious. Although per capita farming area and the educated degree are not the factors affecting non-agricultural employment of rural labor force, the education and training issue of rural labor force and the contradiction between the peasants and land should still be solved.