Abstract: The structure of four single crystals of relaxor ferroelectric of nominal composition PbNi1/3Ta2/3O3 have been studied by single-crystal X-ray diffraction at room temperature (cubic perovskite structure, space group unit cell parameter a = 4.0287–4.0318 Å for different single crystals, refined to agreement factors R1 = 1.05–1.62%). The structural peculiarities (shift of the Pb atom from the ideal perovskite Wyckoff position 1a (0, 0, 0) by ~0.23 Å due to disordering of the atoms over six close-spaced Wyckoff sites 6e (x, 0, 0) along 〈100〉, deviation of the composition from the nominal one, etc.) are discussed.