Catalytic steam reforming of glycerol, a byproduct of the biodiesel industry, is a candidate technique for sustainable hydrogen (H-2) production. Steam reforming of glycerol to produce hydrogen is a potential method to produce hydrogen from biosources. The current work focuses on the synthesis and comparison of two novel catalysts, viz., Ni-Cu/La2O3-MgO and Ni-Co/La2O3-MgO, prepared by coprecipitation (CP) and impregnation (IP) techniques. The synthesis procedures were evaluated in terms of glycerol conversion, H-2 yield, and time on stream (TOS) studies. The results so obtained revealed that the CP method was effective for producing superior H-2 quantity owing to better metal anchorage with support and high surface area. Further, both the catalysts prepared by CP exhibited satisfactory activity and stability. On optimization, both the catalysts reported enhanced H-2 concentration with Ni-Cu/La2O3-MgO reporting the highest H-2 of 96.1 mol % at 773 K and S/C of 9 mol/mol. In addition, both the catalysts demonstrated multicycle durability, thus making them potential materials for large scale application. Finally, a catalytic reaction mechanism was suggested.