Three materials containing N(i)2P, Ni12P5, and Ni3P phases on silica gel with surface area 320 m(2)/g at loadings of 32-37 wt % and the crystal size of NixP phases 30, 9, and 13 nm, respectively, were prepared by a combination of impregnation and TPR methods and tested in hydrodesulfurization (HDS) and adsorptive desulfurization (ADS) of diesel fuel. There were established opposite trends in changing the DS efficiency in two processes: The HDS rate constant decreased while the ADS sulfur capacity (breakthrough at 1 ppmw) increased with increasing the Ni to P ratio in Ni,P from 2 to 3. The observed behavior was attributed to the specific features of the densities of states (DOS) obtained from the density functional theory calculations of total and partial DOS for Ni and P in NixP phases and revealed in XPS measurements of binding energy of Ni 2p(3/2)- and P 2p-electrons. This attribution was consistent with the analysis of the relative part of d-electrons of Ni participating in bonding with p-electrons of phosphorus in these phases.