The Belt and Road Initiative (BRI) countries are mainly developing countries with severe energy poverty. This study combines the entropy weight and the Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS) method to measure energy poverty at the household, enterprise, and national levels in 82 BRI countries. This study aims to investigate and discuss how to encourage BRI countries to develop effective decision-making mechanisms for developing more targeted supply-side solutions to domestic energy poverty. A geographic information system (GIS) is also used to construct spatial distribution maps to assess energy poverty. The findings show that countries in South Asia, Southeast Asia, and North Africa have the highest levels of energy poverty, while countries in West Asia and Europe have the lowest. East Timor, Tonga, and Equatorial Guinea are of the most extremely lowest. The assessment methodology used in this paper focuses not only on the energy poverty faced by households, but also on the overall energy supply and service situation at the enterprise and national levels. These perspectives are likely to influence policy making and help the governments in addressing domestic energy poverty more effectively from the supply side.