The invention discloses a hydrogenation catalyst, which is a phosphor-doped porous carbon material, wherein the specific surface area is greater than 700cm<2>/g; phosphor accounts for 1.4-10% of total mass; and one part of phosphor element in the catalyst has a characteristic peak at 132.5eV in an X-ray photoelectron spectroscopy. The invention further discloses a preparation method of the hydrogenation catalyst and an application for selective hydrogenation reaction of substituent-containing nitro-aromatics.