This study investigates the effect of participation in the Global Value Chain (GVC) on Multidimensional Energy Poverty (MEPI), and the role played by the quality of institutions (QI) in the short and long run for 51 African countries over the period 1995–2018. For this purpose, the DCCE-PMG approach is employed, as well as both the GVC and QI indices. MEPI includes electricity, clean fuel, and technology for cooking. The findings show that GVC participation negatively affects MEPI in both the short and long run, meaning that the GVC reduces energy poverty in Africa. Besides, there is mixed evidence regarding the heterogeneity effect according to rural and urban locations. The evidence further shows that GVCs interact with institutions to negatively impact both energy poverty and the rural–urban MEPI gap, implying that the better the institutional quality, the larger the effect of GVC integration on energy poverty reduction. Therefore, a better quality of institution enables local firms, participating in the GVC, to easily capture technology and knowledge diffusion to promote energy development and fulfill the spatial inequality in energy poverty. Additional tests allow us to confirm the evidence and, moving forward, the implications of participation in the GVC.