In this paper, the effect of interfacial sites between Pd particles and Nb<
sub>
2<
/sub>
O<
sub>
5<
/sub>
species is investigated by testing a series of Pd-Nb<
sub>
2<
/sub>
O<
sub>
5<
/sub>
/SiO<
sub>
2<
/sub>
catalysts with different niobium loadings for the HDO reaction of phenol in the gas phase. Important differences in the selectivity to deoxygenated product were observed depending on the presence of niobium oxide close to Pd particles, which reveals the key role of the type of active phase in the control of reaction steps. It was found that Pd/SiO<
sub>
2<
/sub>
catalyst promotes hydrogenation pathways, producing cyclohexanone as the major product. For Pd-Nb<
sub>
2<
/sub>
O<
sub>
5<
/sub>
/SiO<
sub>
2<
/sub>
catalyst containing a Nb/Pd molar ratio of 0.5, a sharp increase in the selectivity to benzene is observed (7.5-fold). Increasing the Nb/Pd molar ratio, the formation of benzene is enhanced. The results showed that the Pd-Nb<
sub>
2<
/sub>
O<
sub>
5<
/sub>
interface, composed by an oxophilic oxide in the perimeter of the metal particle, is responsible for the activation of the Csingle bondO bond, promoting the deoxygenation reaction.