The inevitable depletion of fossil resources and the resulting anthropogenic climate change require a shift towards renewable feedstocks and eco-friendly technologies for greener energy, fuel, and chemicals production. This mini-review highlights our relevant research contributions to advance the production of carbon-neutral propylene, 1,2-propanediol and biohydrogen through thermo-chemical conversion of biomass-derived glycerol, using various heterogeneous catalysts. These achievements, recently recognized by the “ACI/NBB Glycerine Innovation Award,” are organized into shared sections: (i) economic and environmental benefits of utilizing surplus bioglycerol, as feedstock, (ii) strategies to improve the properties of transition metals-based catalysts (e.g., Pt, Pd, Ni, Cu or Mo supported on γ-Al2O3 or SiO2) for glycerol conversion via: steam reforming, aqueous-phase reforming, hydrogenolysis, and hydrodeoxygenation reactions, (iii) discussion on the catalytic roles of metallic, acidic and/or redox sites, and keys factors affecting catalyst stability and selectivity in these reactions operated under H2O-rich conditions, and (iv) assessment of reaction configurations and operating conditions for improved glycerol conversion into the target product, H2 utilization efficiency and CO2 emissions. The insights aim to guide the continuous improvement of bioglycerol upgrading processes.