Under the condition of “double” surplus of the quantity and quality of rural labors, the high quality development of non-agricultural sector may trigger the choice of high skill labors generated by non-agricultural transfer of rural labors and is not conducive to human capital accumulation of agricultural sector. The analysis based on skill-post matching model shows that under the condition of skill-post positive sorting matching, farmer organization management can provide effective skill-post matching for rural labors by promoting post complexity of agricultural sector as original “skill surplus”, and further mitigate the excessive runoff of high skill rural labors so as to decrease the selection of non-agricultural transfer of rural labors. Based on the data of China Labor Force Dynamic Survey (CLDS) in 2012, in 2014 and in 2016, the analysis reveals that present China’s non-agricultural transfer of rural labors really has the selection for high skill labors, however, the construction of farmer cooperatives can really inhibit their non-agricultural transfer behavior by promoting skill-post matching efficiency of high skill labors in the agricultural sector and further decrease the selection of non-agricultural transfer of rural labors. Thus, agricultural sector should realize high quality development by the method of organization management and so on while non-agricultural sectors transform into high quality development. In the process of boosting farmer cooperative development, we should appropriately pay attention to promoting post complexity, and ensure the implementation of skill-post positive sorting matching and its matching efficiency reward in order to effectively decrease the selection of non-agricultural transfer of rural labors and boost the accumulation and structure optimization of rural human capital.