Based on the density functional theory, the initial configurations of cluster Ni₄P were optimized and calculated at B3LYP/Lanl2dz level, and its stable configurations were obtained. The bond formation of stable configurations is analyzed from the bond length, bond order and orbital hybridization between atoms. The results are as follows:there is an antagonism between Ni—Ni bond and Ni—P bond, Ni—Ni bond formation is affected by spatial configuration. However, the bond order of Ni—P is not affected by the spatial configuration and spin multiplicity. On the whole, the Ni—P bond is the main contributor to the stability of each configuration, and the bonding contribution of each configuration is not affected by spin multiplicity; the contribution of Ni atom to orbital hybridization is greater than that of P atom; the d-p hybridization and p-p hybridization exist between the Ni and P atoms. In addition, there are s-p-p hybridization between Ni and P atoms of configuration 1⁽⁴⁾ ~2 ⁽²⁾, and p-p-d hybridization between Ni and P atoms of configuration 3⁽⁴⁾ and 3⁽²⁾.