The dependences of relative dielectric permittivity, e′r, and tangent of dielectric loss angle, tg δ, of gallium phosphide (GaP) nanosolid on frequency and temperature were investigated. The GaP nanopowders are subglobular in shape, with the average crystallite size of about 50 nm evaluated from Scherrer equation. It can be concluded that the leakage current mechanism plays an important role in the dielectric loss of the GaP nanosolid. The dielectric characteristic of the GaP nanosolid in the range 298–350 K allows to detect an e′r or tg δ peak at 303 K that is due to local phase transitions, probably in the high hydrostatic stress field of dislocations with an edge component. Under the influence of an electric field, the high hydrostatic stress field of dislocations can undergo changes in deformation, accompanied by drastic stress-induced changes in the order parameter near the phase transition temperature, and hence, changes in the Gibbs free energy per unit volume can be found.