To meet the requirement of high catalytic efficiency toward the reduction of p-nitrophenyl compounds, we designed a new one-dimensional Fe3O4/FeNi embeddednanostructured catalyst synthesized by a one-pot controlling growth-reduction process in a solvothermal system, in which Fe3O4 phase was implanted in the base of FeNi alloy. In the Fe3O4/FeNi catalyst system, the Fe3O4 embedded phase attracts the nitro group of p-nitrophenyl compounds by its high-density electrons, which can efficiently promote the activity of amorphous FeNi active centers for selective catalysis toward the reduction of a range ofp-nitrophenyl compounds. Moreover, for the para-group in the nitrophenyl compounds, an increasing electron-donating power contributes to a higher catalytic activity, while electron-withdrawing power obtains the reverse case. Additionally, the Fe3O4/FeNi composite nanocatalyst exhibited an outstanding cycling performance over 20 times without obvious performance decay. This work opens an avenue to design more powerful non-noble metal catalysts for green chemistry.