In summary, we have developed highly efficient, chemo-selective thin layers graphene encapulcatulted Ni@C and Pd@C catalysts as new catalysts for active and selective hydrogenation of challenging 4-nitrostyrene to 4-vinylaniline, 4-ethylbenzenamine, and 1-ethyl-4-nitrobenzene separately. The solvent, pyrolysis temperature, and oxidation step had a great effect on the catalyst physical properties, catalytic activity, and product selectivity. The most efficient catalyst Ni/NiO@-700-200-1-H2O prepared from solvent H2O, 700 °C pyrolysis temperature, and oxidation step, could achieve >99% 4-VA selectivity at 100% conversion of 4-nitrostyrene. The reaction conditions of solvent, reaction temperature, and H2 pressure affect the product distribution significantly. In non-polar solvent toluene, the Ni@C catalyst is more active for the -NO2 than C=C, but in the polar, protic solvent EtOH, it can hydrogenate both -NO2 and C=C groups. The prepared N-doped Pd@C has unique properties compared with commercially available Pd/C and Pt/C, can only hydrogenate the C=C without hydrogenating NO2, and give the 4-ENB an excellent yield of 99%. And more interestingly, the active catalysts wearing graphene "bulletproof vests" have excellent stability and can be applied in advanced industrially applicable flow reactors for the three products synthesis separately with excellent yield by simple switching different control valves.