Recently, it has been reported that the enstatite chondrite (EC) meteorite may contain enough hydrogen to provide a plausible explanation for water's initial existence on Earth. Perryite mineral is one of the key components of EC, but its detailed chemical composition and phase width remain elusive compared with other minerals found in EC. Therefore, we embark on a series of investigations of the synthesis, crystal structure, and electronic structure of the synthetic perryite mineral (NixFe1-x)8(TyP1-y)3 (T = Si and Ge; 1 ≥ x, y ≥ 0). Its crystal structures were established based on single-crystal and powder X-ray diffraction techniques. It is realized that its structural and phase stabilities are highly dependent on the nature of the doping element (i.e., Fe and Si). The inclusion of Si and Fe elements can greatly alter the bonding scheme near the Fermi level (Ef), which is vital to the phase stability and accounts for the chemical composition of the natural perryite mineral (quaternary compound) in EC meteorites. Furthermore, this phase exhibits good electrocatalytic activity toward the hydrogen evolution reaction (HER). The best and the worst HER performances are for the Ni8Ge2P and Ni8Si2P samples, respectively, which suggests that the long bond length and high polarity of the covalent bond are the preferred criteria to enhance the electrocatalytic HER in this series.