A single crystal of tetrachloro(0,0-pivaloylato)antimony(V) has been studied at 77 K, by Zeeman perturbed ³⁵ Cl NQR, using a FT-NQR pulsed spectrometer. The four lines at zero-field, ν₁ = 27.6468, ν₂ = 27.3070, ν₃ = 25.7341 and ν₄ = 25.3438 MHz yield eight EFG tensors in the magnetic field, related by a twofold symmetry element in the crystal. The corresponding asymmetry parameters are η₁ = 0.134, η₂ = 0.13, η₃ = 0.07, and η₄ = 0.09. The molecular structure deduced from the relative orientations of the principal Z-axes of the EFG tensors confirms that the higher quadrupole coupling constants are associated with the chlorine atoms in equatorial positions, relative to the plane of the organic ligand, as predicted from NQR powder studies. It is concluded that the crystal structure is monoclinic with two (class m or 2) or four (class 2/m) molecules per unit cell. The molecular packing is such that the planes formed by equatorial or axial chlorine atoms are approximately at right angles to their symmetry related images.