Global emission statistics show that Africa is among the least carbon-emitting continents. However, the rising drive for economic growth amid urbanization and globalization in recent years has continued to attract the attention of policymakers to the attendant potential environmental risks. Hence, using robust empirical techniques, this study examines the impacts of increasing urbanization alongside its interactions with energy portfolios on environmental prospects of 15 selected African countries including the most urbanized and leading oil producers in the continent of Africa. The results of the analysis produced insightful implications for achieving both environmental and economic sustainability for the understudied countries. Firstly, the trio of urbanization, economic globalization, and income levels aggravate environmental degradation among these countries as they were found to be essential drivers of carbon emission levels over the understudied period (1990–2015). Secondly, while urbanization significantly poses threat to environmental sustainability, the evidence obtained regarding its interaction with energy portfolios of the understudied countries differs. The significant detrimental environmental impacts of the interaction between urbanization and energy portfolios were only confirmed in the context of fossil energy consumption among the countries, while renewables exist as a significant decarbonization channel within the framework of the increasing level of urbanization among the countries. Thirdly, the study upholds the EKC conjecture. Hence, policymakers and authorities in Africa should capitalize on maximizing the benefits of the huge renewable resource potentials on the continent through adequate investments in green energy technologies for urban infrastructures toward the realization of sustainable development goals (SDGs 11 and 13).