High-density (>98% of full density) nanocrystalline invar alloys with significantly enhanced hardness (>240 in Vicker’s hardness) were prepared by sintering compacted Fe-Ni nanoparticles in hydrogen. The precursor Fe-Ni nanoparticles were synthesized by hydrogen plasma evaporation of bulk Fe61Ni39 alloys. The size and the productivity of the Fe-Ni nanoparticles increased with increasing hydrogen pressure. The presence of surface oxidation of the Fe-Ni nanoparticles when exposed to air was proved by the X-ray photoelectron spectra measurements. The compacted Fe-Ni nanoparticles grew rapidly at 956 °C, while the oxide impurities were removed completely by following hydrogen at 735 °C, which was found to be optimum for the synthesis of oxide-free nanocrystalline metals with fine grain size. The typical hardness of an invar alloy prepared by melting method was around 140 HV. The significantly enhanced hardness of our nanocrystalline invar alloys was potentially important in strengthening the durability of its components in instruments and in improving its machinability when machining for a component.