The implementation of the 10-year fishing ban compensation policy in the Yangtze River basin is the first practice of the river ecological compensation project in China, which has a milestone value to protect China’s ecological sustainability and boost green development. Based on the survey data of 212 retired fishing households in Ma’anshan city, this paper constructs a livelihood capital evaluation system, coupled with coordination model and mobility matrix to analyze the policy effect on participants’ livelihood from the changes of livelihood capital amounts on structure and mobility. The key results are threefold. (1) Policy implementation has significantly raised retired households’ livelihood capital index; (2) The households livelihood capital coupling coordination degree has significantly improved, and the capital structure has transitioned from imbalanced to coordinated; and (3) Households’ livelihood capital exhibits a high mobility, and the gap between rich and poor has been narrowed. This paper theoretically contributes to the research on ecological compensation by providing a more comprehensive perspective of policy effect analysis, and it can also provide a micro level empirical basis for policymakers to optimize the follow-up fishing ban policy