<p>Rural energy poverty poses significant environmental and social problems. Urbanization offers a potential solution by promoting socio-economic development in rural areas. However, the relationship between urbanization and rural energy poverty remains unclear. This study examines the impact of urbanization on rural energy poverty and its mechanisms, alongside the moderating effects of marketization and technological innovation, using fixed effects model and panel quantile model with data from China’s provinces between 2003 and 2018. The results indicate that urbanization significantly alleviates rural energy poverty through improvements in energy infrastructure, particularly in regions with greater energy deficits. Moreover, marketization and renewable energy technological innovations further enhance the positive effects of urbanization. Consequently, policymakers should prioritize urbanization initiatives, alongside supportive marketization reforms and tailored renewable energy strategies, to effectively address the structural challenges of energy poverty in rural areas. This study can help inform the development of more comprehensive responses to rural energy poverty going forward.</p>