The 79-81 Br NQR spectra of tribromocadmates with the cations K ⊕ , NH 4 ⊕ , Rb ⊕ , Cs ⊕ , CH 3 NH 3 ⊕ , (CH 3 ) 2 NH 2 ⊕ , (CH 3 ) 4 N ⊕ , H 2 NNH 3 ⊕ , and C(NH 2 ) 3 ⊕ were studied as functions of temperature from 77 K on up to T>300 K. CsCdBr 3 shows a singlet 81 Br NQR spectrum over the whole temperature range studied. [CH 3 NH 3 ]CdBr 3 , with one 81 Br NQR line spectrum at room temperature, experiences a phase transition at 167 K; below this temperature an 18-line spectrum is observed. In [(CH 3 ) 4 N]CdBr 3 (phase II), at 290 K, a singlet 81 Br NQR is present as is in the high temperature phase III (T II.1 , = 390 K); the low temperature phase III (T II,m , = 160 K has a triplet 81 Br NQR spectrum. KCdBr 3 shows an 81 Br NQR doublet spectrum, as do RbCdBr 3 , [H 2 NNH 3 ]CdBr 3 , and [C(NH 2 ) 3 ]CdBr 3 . 81 Br NQR triplets are observed for [(CH 3 ) 2 NH 2 ]CdBr 3 and NH 4 CdBr 3 . Several crystal structures were determined (at room temperature). [(CH 3 ) 4 N]CdBr 3 : P6 3 /m, Z = 2, a - 940 pm, c = 700 pm, disordered cation, single chain Perovskite with face connected [CdBr 6 ]- octahedra (nearly CsNiCl 3 -type). [(CH 3 ) 2 NH 2 ]CdBr 3 : P2 1 /c, Z = 4, a = 898 pm, 6 = 1377 pm, c = 698 pm, ß = 91.2°, face connected [CdBr 3 -octahedra single chain Perovskite. NH 4 CdBr 3 : Pnma, Z = 4, a = 950 pm, b = 417 pm, c= 1557 pm, with a double chain of condensed [CdBr 6 ]-octahedra, NH 4 CdCl 3 -type. [N 2 H 5 ]CdBr 3 : P 2 ,/c, Z = 4, a = 395 pm, 6 = 1749 pm,c = 997 pm,ß = 94.2°, double chain polyanion similar to NH 4 CdBr 3 . [C(NH 2 ) 3 ]CdBr 3 : C 2 /c, Z = 4, a = 778 pm, 6 = 1598 pm, c = 746 pm, ß = 110.2°, a single chain Perovskite with a chain of condensed trigonal bipyramids [CdBr5]. Three types of anion chains of CdBr 3 have been observed: Single octahedral chains, face connected; double octahedral chains, edge connected; a trigonal-bipyramidal chain, edge connected. The relation between the crystal structure and the Br NQR is discussed