The economic and environmental implications for fuels production from fossil sources have stimulated developments in renewable energy technologies. Specifically, within the past decade, a 500-fold increase in biodiesel manufacture has been recorded in US alone. This has however, led to a market glut in glycerol–a by-product of biodiesel synthesis. In this study, we examine the thermodynamic ramifications of hydrogen (a clean fuel) production from the steam reforming of glycerol. The main reaction is endothermic and may be accompanied by other side reactions. The H₂ yield is a function of the operating temperature, pressure and reactant ratio (steam-to-glycerol ratio, STGR). Thus, the conditions which offer maximum H₂ yield and product ratio (H₂:CO₂ and H₂:CO) was investigated using the minimization of the Gibbs free energy. The components assumed in the equilibrium mixture for the analysis are C₃H₈O₃, H₂O, CO₂, CO, H₂, CH₄, C₂H₄, C₂H₆, C₃H₆ and C₃H₈. Results showed that CO₂ formation is favoured at low temperatures (550K–650K) and somewhat insensitive to the STGR, while H₂ production is more facile under high STGR and temperature. As expected, CO yield is more thermodynamically feasible at high temperature and relatively low STGR (< 1). Low CH₄ production at high temperature and STGR is indicative of the simultaneous steam reforming of the intermediate product and indeed, similar results (not shown) were obtained for C₂₊ hydrocarbons. Implications of this thermodynamic analysis in the context of GTL conversion and higher alcohols synthesis are discussed in the full paper.