Due to the pressing need to attain sustainable development goal 7, global attention on addressing energy poverty has increased. Improving rural education has been recognized as a strategy to mitigate energy poverty in rural China. However, the presence of education inequality remains a substantial challenge to energy poverty alleviation and underexamined. Our research aims to evaluate rural energy poverty levels systematically and investigate the impact of education inequality on rural energy poverty. This study begins by employing a novel weighting approach to develop a comprehensive indicator system, which accurately measures the extent of energy poverty in rural China. Subsequently, a panel fixed-effects model is utilized to analyze the causal impact of education inequality on rural energy poverty. Furthermore, the study explores the heterogeneity and potential mechanisms of education inequality on rural energy poverty. Findings reveal a decline in rural energy poverty from 2005 to 2020, and the nature of energy poverty has substantially transformed, with a greater prominence of using unclean and unaffordable energy sources. Education inequality increases rural energy poverty and indirectly affects it by reducing the income of rural residents. The influence of education inequality on rural energy poverty exhibits heterogeneity in both time and region. Policy recommendations are proposed for mitigating energy poverty and promoting education equality in rural areas.