Phosphorous-doped NiMo/Al2O3 hydrodesulfurization (HDS) catalysts (nominal Mo, Ni and P loadings of 12, 3, and 1.6 wt%, respectively) were prepared using ethyleneglycol (EG) as additive. The organic agent was diluted in aqueous impregnating solutions obtained by MoO3 digestion in presence of H3PO4, followed by 2NiCO(3)center dot 3Ni(OH)(2)center dot 4H(2)O addition. EG/Ni molar ratio was varied (1, 2.5 and 7) to determine the influence of this parameter on the surface and structural properties of synthesized materials. As determined by temperature-programmed reduction, ethyleneglycol addition during impregnation resulted in decreased interaction between deposited phases (Mo and Ni) and the alumina carrier. Dispersion and sulfidability (as observed by X-ray photoelectron microscopy) of molybdenum and nickel showed opposite trends when incremental amounts of the organic were added during catalysts preparation. Meanwhile Mo sulfidation was progressively decreased by augmenting EG concentration in the impregnating solution, more dispersed sulfidic nickel was evidenced in materials synthesized at higher EG/Ni ratios. Also, enhanced formation of the so-called "NiMoS phase" was registered by increasing the amount of added ethyleneglycol during simultaneous Ni-Mo-P-EG deposition over the alumina carrier. That fact was reflected in enhanced activity in liquid-phase dibenzothiophene HDS (batch reactor, T = 320 degrees C, P = 70 kg/cm(2)) and straight-run gas oil desulfurization (steady-state flow reactor), the latter test carried out at conditions similar to those used in industrial hydrotreaters for the production of ultra-low sulfur diesel (T = 350 degrees C, P = 70 kg/cm(2), LHSV = 1.5 h(-1) and H-2/oil = 2500 ft(3)/bbl). (C) 2008 Elsevier B.V. All rights reserved.