The thermal decomposition of sparingly soluble crystalline complex salts formed in the solution of bismuth(III) bromide and hydrobromides of pyridine, 3-methylpyridine, 2,6-methylpyridine, 2-aminopyridine, 4-aminopyridine and piperidine in 40% hydrobromic acid has been studied. Thermal analysis curves (DTA, TG, DTG) are presented. In the course of decomposition, the corresponding amine or its decomposition products, HBr and BiBr3, are liberated. The effect of the basicity of the amide on the melting temperature and thermal stability of the compounds was determined. A comparison with analogous complexes of antimony(III) and arsenic(III) is made.