Although HDS and HDN reactions over transition metal phosphides have been widely studied, few publications about aromatic hydrodearomatization (HDA) over transition metal phosphides are found. Using ordered mesoporous Al-MCM-41 (Al-M) as the support, a series of supported nickel phosphide catalysts with different Ni/P molar ratios and loadings have been prepared by a temperature-programmed reduction and characterized. The HDA activity of naphthalene was measured in a fixed bed reactor at 250–330 °C and 3 MPa. The results showed that the catalyst with initial Ni/P molar ratio of 1.25 and 15 wt% loading displayed the highest HDA activity as well as 99.0% of selectivity of decalin at 270 °C, which is even higher than that of 0.5 wt% Pt–Al-M catalyst. As a comparison, the HDA performance of various catalysts was also examined. The results revealed that the presence of framework aluminum favors HDA processes and a synergistic effect between nickel phosphide and the suitable acidity resulted in an improvement of the catalytic activity. Finally, the possible reaction pathway of naphthalene hydrogenation (HYD) on nickel phosphide catalysts was proposed. Taking into consideration the high catalytic activity, Al-M supported nickel phosphide can be considered as a very efficient HDA catalyst to decrease the contents of aromatics in the fuels.