Temperature dependence of 35Cl NQR frequencies in TeCl4･POCl3 giving six NQR lines was observed in the range of 77 K to 400 K. Three of the NQR iines faded out near 285 K and the others could be detected up to 360 K. The Zeeman effect on the resonance lines was examined at 253 K using a single crystal. Each of these lines gave a single zero-splitting pattern and all the asymmetry parameters for these lines were negligibly small. On the basis of the crystal symmetry and the orientations of the Te-Cl and P-Cl bonds, the moiecular structure of the title compound was deduced and the assignment of the NQR lines was performed with the aid of a CND0/2 MO calcuiation.