The reaction of 4-phenyl-2-aminothiazole or 2-amino pyridine with α-bromo acetic (–)-menthyl ester (2c) yields new N-alkyl cycloimmonium bromides (1c, 3) with the chiral (–)-menthyl substituent, which were isolated and fully characterized by 1H and 13C NMR spectroscopy for the first time. In addition, starting from 4-phenyl-2-aminothiazole, two further N-alkyl cycloimmonium bromides (1a, 1b) were prepared. The molecular and crystal structures of all three thiazole derived N-alkyl cycloimmonium bromides (1a–c) were determined by single-crystal X-ray diffraction. In all cases the crystal structures are dominated by N–H···Br hydrogen bonds, which results in the formation of an extensive hydrogen bonded network in the crystal. Interestingly, in all structures S···Br– distances shorter than the sum of the van der Waals radii are observed.