A comparative study has been performed on Ni₂P/SiO₂ catalysts prepared by: (i) conventional temperature-programmed reduction (TPR) of calcined precursors following wet impregnation of the support, (ii) TPR of a sol–gel prepared NiO/SiO₂ precursor impregnated with NH₄H₂PO₄ and (iii) a solution-phase reaction in the presence of the SiO₂ support using Ni(acac)₂ and trioctylphosphine. Catalyst characterization shows that the Ni₂P prepared by the solution-phase method has a uniform particle size (7.5 ± 0.8 nm) and H species can easily transfer from the nickel sites to the SiO₂ support on this catalyst. These properties result in a high NaBH₄ methanolysis to hydrogen activity. In contrast, the sol–gel prepared Ni₂P/SiO₂ has a relatively high catalytic activity for phenol hydrodeoxygenation due to a higher concentration of Ni^δ+ species that act as Lewis acid sites and metal sites, and a higher Ni₂P crystallinity.