This paper discusses how the existing 1.2 billion poor people worldwide without access to electricity can be environment-friendly electrified with the implementation of the UN Sustainable Development Goal 7 (SDG7) on energy and the 2015 Paris Agreement on climate change. The objective of this paper is to demonstrate the experience of the Global Environment Facility (GEF) in rural electrification with renewable energy-based microgrids or mini-grids, and identify challenges and business opportunities in rural electrification in the least developed countries (LDCs). Several case studies are presented to show GEF’s strategies of financing renewable energy-based microgrids. This paper concludes that (1) with the demonstrated evidence of the importance of new technologies for renewable energy-based microgrids, it is necessary to improve enabling environments for creating markets conducive to the new technologies; (2) project investment is a necessary first step, but for success to be fully realized, catalyzing follow-on investments should also be set as an important goal; and (3) investments need to include effective technology transfer components for renewable energy-based microgrid technologies.