Compared to air, rail, and road transport, shipping is a more energy-efficient and environmentally friendly way to transport goods over a long distance. However, the unprecedented growth of global seaborne trade has had a significant impact on the environment. The process of shipping transportation, through exhaust gas, wastewater discharge, fuel leakage, etc., has caused very serious environmental pollution. In response to this issue, the International Maritime Organization introduced the International Convention for the Prevention of Pollution from Ships (MARPOL) Convention to regulate the discharge of pollution from ships. Given that there are few studies discussing policy effectiveness, this study comprehensively considers and reviews the implementation effectiveness of all annexed policies under the MARPOL Convention. After discussing the differences between these policies based on the implementation conditions, requirements, strictness, and scope of adoption, the empirical analysis method of time-varying differences-in-differences model is adopted to analyze the policy effectiveness of each annex. It further puts forward suggestions and references for the formulation of effective maritime policies in the future that should be targeted, comprehensive, contingency-based, and proactive. This will help design or revise policies in the shipping industry, thereby promoting the early achievement of shipping emission reduction targets and contributing to the sustainability of the shipping industry.