Waste sorting is the cardinal measurement to solve the problem of low efficiency of rural environmental governance and to alleviate environmental pollution by reduction, recycling, and harmlessness in rural areas. However, non-excludable and non-rival features of public goods easily cause a wide free-rider problem, which results in a low frequency of participation in the waste sorting of rural people. Based on the theory of the utility maximization of the rational economic man, this paper investigates survey data of 688 farm households in three cities and three counties of Shaanxi Province to explore the effect of the perceived value on the household waste classification behavior based on cost-benefit analysis. The results show that perceived benefit and perceived cost are important perceived value factors affecting farmers’ participation in waste sorting. Specifically, the spiritual benefit of the perceived benefit has a significantly positive impact on classification behavior, while the time cost, physical cost, and material cost of the perceived cost have a negative impact on waste classification behavior. Further study of the heterogeneity of income impact shows that time cost only has a significant impact on the high-income group of farmers’ classification behavior, while spiritual benefit and learning cost only affect the low-income group of farmers’ waste classification behavior. Material cost has different influence directions on high- and low-income groups. In view of the aforementioned findings, this study highlights corresponding policy implications from the perspective of perceived benefit and perceived cost.