The compounds [quinolinium] 4[Bi 2Cl 10] ( 1), [isoquinolinium] 4[Bi 2Cl 10] .2H 2O ( 2) and [8-hydroxyquinolinium] 4[BiCl 6]·Cl·2H 2O ( 3) have been obtained by reacting bismuthate oxide and the appropriate base in HCl acid medium. The crystal structures of 1 and 2 consist of quinolinium and isoquinolinium cations, respectively, interacting through hydrogen bonding with [Bi 2Cl 10] 4− dimers. The different degree of interactions in the two derivatives causes significant differences in the bond distances of the anions. The crystal structure of 3 is made of [BiCl 6] 3− and Cl − anions and 8-hydroxyquinolinium cations. Hydrogen bond interactions including the N-bonded and O-bonded H atoms together with an interstitial chlorine atom stabilize the entire crystal structure.