The present invention belongs to the field of application technology of skeleton nickel, and is especially high selectivity catalytic process of hydrogenating methoxyl nitro compound to produce methoxyl aniline. Under mild condition, methoxyl nitrobenzene is hydrogenated selectively in the presence of catalyst. The main catalyst has precursor of NiAlM alloy prepared through high temperature melting and quenching, with the modifying component M is one of Fe, Mn, Mo, Cr and W, or their proper combination. The precursor is activated in water solution of NaOH to eliminate Al to form skeleton nickel-base catalyst with very high hydrogenating activity and selectivity. Methoxyl aniline may be prepared through one-step reaction in yield over 99 %, and the preparation process has high selectivity, stable catalyst activity, long catalyst service life, reuseability of the catalyst and low cost.