Crude glycerol is the main byproduct of biodiesel manufacturing from oleaginous crops and other biomass-derived oils. Approximately 10% crude glycerol is produced with every batch of biodiesel. Worldwide, there is a glut of glycerol and the price of it has decreased considerably. There are real opportunities for valorizing crude glycerol into higher value-added chemicals which can improve the economic viability of biodiesel production as an alternative fuel. Exploring new potential applications of glycerol in various sectors is needed such as in pharmaceuticals, food and beverages, cosmetics, and as a transportation fuel. However, crude glycerol produced directly from biodiesel often contains impurities that hinder its direct industrial usage and thus, a refining process is needed which is typically expensive. Hence, this review reports on current upgrading crude glycerol technologies—thermo-, bio-, physico-, and electrochemical approaches—that valorize it into higher value-added chemicals. Through comparison between those viable upgrading techniques, future research directions, challenges, and advantages/disadvantage of the technologies are described. Electrochemical technology, which is still underdeveloped in this field, is highlighted, due to its simplicity, low maintenance cost, and it working in ambient condition, as it shows promising potential to be applied as a major glycerol upgrading technique.