The forming of ordering structure in NiCrAlFe precision alloy is a vital factor for the electrical properties. Using the first-principles pseudopotential plane-wave method, the lattice constants, binding energies and density of states of an NiCrAlFe precision resistance alloy were calculated based on the disordering solid solution and L12-type ordering structures. The microstructure of the alloy was analyzed by high-resolution transmission electron microscope (HRTEM), also, the electrical resistance of the alloy was measured after solid-solution and aging treatment. From the binding energy point of view, the ordered structure is more stable than the disordered solid solution. The calculation results of density of states show that in the ordered structure, Ni, Cr, Al and Fe atoms bond with each other more strongly than they do in the disordered solid solution, and thus the stability of the alloy is improved. In fact, ordering structure with L12-type was revealed by HRTEM in the as-aged alloy, and its lattice parameter is close to the calculated result. According to the comparison of density of states at the Fermi level of different structures, the electrical conductivity of the alloy will decrease due to the formation of L12 ordered structure from the disordered solid solution, which is consistent with the experimental results.