In recent decades, the use of biomass as alternative resources to produce renewable and sustainable biofuels such as biodiesel has gained attention given the situation of the progressive exhaustion of easily accessible fossil fuels, increasing environmental concerns, and a dramatically growing global population. The conventional transesterification of edible, nonedible, or waste cooking oils to produce biodiesel is always accompanied by the formation of glycerol as the by-product. Undeniably, it is essential to economically use this by-product to produce a range of valuable fuels and chemicals to ensure the sustainability of the transesterification process. Therefore, recently, glycerol has been used as a feedstock for the production of value-added H2 and chemicals. In this review, the recent advances in the catalytic conversion of glycerol to H2 and high-value chemicals are thoroughly discussed. Specifically, the activity, stability, and recyclability of the catalysts used in the steam reforming of glycerol for H2 production are covered. In addition, the behavior and performance of heterogeneous catalysts in terms of the roles of active metal and support toward the formation of acrolein, lactic acid, 1,3-propanediol, and 1,2-propanediol from glycerol are reviewed. Recommendations for future research and main conclusions are provided. Overall, this review offers guidance and directions for the sufficient and economical utilization of glycerol to generate fuels and high value chemicals, which will ultimately benefit industry, environment, and economy.