Guanidinium hexabromoantimonate(V) [C(NH2)3]SbBr6 was prepared. It was black in color at room temperature and showed a tendency to turn yellow by loosing bromine in open air. Six 81Br NQR lines were observed at 77 K. On heating, four of the six lines faded out around 200 K, while the remaining two lines could be observed up to room temperature. This temperature behavior suggests a preferential libration or reorientation around a pseudo C4 axis of the octahedral [SbBr6]- anion. DTA measurement revealed a small heat anomaly at Tcl = 273 K (on heating), showing a thermal hysteresis, and a sharp and large anomaly at Tc2 = 314 K. The temperature dependence curve of 1H NMR T\\ is characterized by a single minimum of 26 ms (32 MHz) near 280 K, which is assigned to the C3 reorientation of the planar [C(NH2)3]+ cations. Its activation energy (-Ea) is 43.3 kJ/mol. © 2014, Verlag der Zeitschrift für Naturforschung. All rights reserved.