Perryite, natural Ni-silicide, is a minor but regular constituent of the metal phase in enstatite chondrite (aubrite) and enstatite chondrite meteorites. Its synthetic analog was shown to have promising catalytic properties. The first-time solution of the crystal structure of natural perryite was completed on the material from the Mount Egerton aubrite. The mineral is trigonal, R¯3c, a = 6.6525(5), c = 37.998(5) Å, V = 1456.3(3) and Z = 6. The structure was refined to R₁ = 0.0137 based on 457 independent observed reflections. The chemical formula obtained from the structure refinement, (Ni_14.14 Fe_1.88 )_Σ16.02 PSi₅, agrees with that derived from the electron microprobe data, (Ni_13.39 Fe_2.65 Co_0.01 )_Σ16.05 P_1.22 Si_4.74 . This research showed that P and Si in perryite are ordered, resulting in the simplified formula (Ni,Fe)₁₆ PSi₈, in contrast to the currently accepted variant (Ni,Fe)₈ (Si,P)₃ . The detailed results of EBSD study reveal previously unknown relationships between perryite, associated α-(Fe,Ni) metal (also known as kamacite) and schreibersite, (Fe,Ni)₃ P. Since enstatitic meteorites represent the early stages of nebular accretion, our results demonstrate that the crystal-chemical factor could affect the differentiation of chemical elements upon the onset of the Solar System formation.