The use of biomass to produce transportation and related fuels is of increasing interest. In the traditional approach of converting oils and fats to fuels, transesterification processes yield a very large coproduction of glycerol. Initially, this coproduct was largely ignored and then considered as a useful feedstock for conversion to various chemicals. However, because of the intrinsic large production, any chemical feedstock role would consume only a fraction of the glycerol produced, so other options had to be considered. The reforming of glycerol was examined for syngas production, but more recently the use of photocatalytic decomposition to hydrogen (H-2) is of major concern and several approaches have been proposed. The subject of this review is this greener photocatalytic route, especially involving the use of solar energy and visible light. Several different catalyst designs are considered, together with a very wide range of secured rates of H-2 production spanning several orders of magnitude, depending on the catalytic system and the process conditions employed. H-2 production is especially high when used in glycerol-water mixtures.