Abstract: Eco-compensation for the comprehensive utilization of straw is designed to encourage households to actively participate in a government program on straw returning to cropland for green development of agriculture. However, there is no consensus on whether eco-compensation for comprehensive utilization of straw promotes households’ adoption of straw returning. This study explored the impact of eco-compensation for comprehensive utilization of straw on households’ adoption of straw returning, which is of great significance in solving the dilemma of repeated straw burning and realizing the development of green, low-carbon, and circular agriculture. Based on the Stimulus-Organism-Response model and the Motivation-Opportunity-Ability model, this study formulated an analysis framework of eco-compensation for comprehensive utilization of straw and households’ behavior of straw returning to explore the influence of eco-compensation, internal perception, and social capital on households’ straw returning behavior. In our empirical study, 822 households in Huanggang City, Hubei Province, were interviewed using a questionnaire. A Binary Probit model was used for empirical testing. The results showed that: 1) after considering the possible endogeneity and measurement errors caused by missing variables, eco-compensation for comprehensive utilization of straw had a significant positive impact on the straw-returning behavior of households. Specifically, subsidies played a more significant role in promoting straw-returning behavior by households than supervision and penalties. This conclusion was supported by the robustness tests. 2) Households’ internal perception produced a mediating effect on the impact of eco-compensation for comprehensive utilization of straw on the straw returning behavior. Namely, eco-compensation for the comprehensive utilization of straw promoted the straw returning behavior by households by improving the internal perception of straw-returning technology. 3) Household social capital had a positive moderating effect on the relationship between eco-compensation for comprehensive utilization of straw and household straw-returning behavior. Specifically, improvement in social capital further strengthened the promotion of eco-compensation for the comprehensive utilization of straw through straw return by households. The policy implication of our findings is that it is necessary to establish a sound eco-compensation system for the comprehensive utilization of straw, enhance households’ internal perception of straw returning, and improve households’ social capital, to promote the utilization of straw and high-quality development of agriculture.