Iron phosphide catalysts supported on silica with an iron loading of 15 wt% were synthesized and studied in the hydrodeoxygenation (HDO) of phenol. The amount of phosphorus varied in order to obtain iron phosphides with different stoichiometry. Catalysts containing Fe 2 P, FeP and FeP 2 phases were obtained. The textural and structural properties of the prepared catalysts were evaluated by using different experimental techniques such as N 2 adsorption -desorption at -196 ?C, X-ray diffraction (XRD), M?ssbauer spectroscopy, high resolution trans- mission spectroscopy (HRTEM), infrared spectroscopy (IR) of adsorbed CO at low temperature, X-ray photo- electron microscopy (XPS) and NH 3 thermoprogrammed desorption (NH 3 -TPD). The catalytic activity was stu- died at 275 ?C and at 15 and 5 bar of hydrogen pressure in the hydrodeoxygenation reaction of phenol. Characterization results evidenced that the initial P/Fe ratio employed in the synthesis not only governed the stoichiometry of the iron phosphide, but also the particle size, metallic surface exposure and acidity. The cat- alysts presenting unique phases were those presenting better activity in the HDO reaction of phenol. Moreover, Fe 2 P phase presented better results than FeP in terms of HDO conversion.