The polystyrene doped with 2,5-diphenyloxazole as a primary fluor and 2-(4-styrylphenyl)benzoxazole as a wavelength shifter prepared as a plastic scintillator was investigated using positronium probe in wide range of temperatures from 123 to 423 K. Three structural transitions at 260, 283, and 370 K were found in the material. In the