The electronic structure of Ni₂P(0001) has been investigated by photoelectron spectroscopy (PES) utilizing synchrotron radiation. A Ni 3d–P 3p hybrid band was observed at 1-5 eV, and the band had peaks at 1.5 eV and 3.4 eV together with a shoulder around 2.4 eV. The resonant PES study showed that the Ni 3d component was included in the whole binding energy region of the band. The change in the surface electronic structure of Ni₂P(0001) induced by the segregation of P atoms was investigated by annealing temperature-dependent measurements of PES, and it was found that the change proceeded via following two steps: the segregation of P atoms proceeded at about 200°C, and the bonding between surface Ni atoms and segregated P atoms was facilitated at > 300°C. The bonding between Ni and P atoms induced substantial stabilization of Ni 3d levels, which is contrary to the case of Fe₂P(0001) where the segregation of P atoms induced little change in DOS of Fe 3d levels. [DOI: 10.1380/ejssnt.2015.93]