New bismuth(V) complexes with the general formula of Bi ^V R ₃ (O ₂ CR′) ₂ have been synthesized by the reaction of BiR ₃ Cl ₂ with Ag(O ₂ CR′), where R is an aromatic ligand and R′ a substituent containing a hydroxyl group. The role of these new bismuth(V) complexes as building blocks to form hydrogen-bonded extended structures in the solid has been examined by single-crystal X-ray diffraction analyses. The bismuth atoms in these compounds adopt distorted trigonal-bipyramidal geometries. The hydrogen-bonding pattern and the extended structure displayed have been found to be highly dependent on the R and the R′ groups. Unusual hydrogen-bonded extended structures such as double strands and double layers have been observed. In an attempt to obtain chiral helical extended structures, the reactions of BiR ₃ Cl ₂ with several silver salts, Ag(O ₂ CR*), where R* contains one chiral centre and a hydroxyl group, were examined. The bismuth(V) centre shows an unusual stereoselectivity towards the chiral ligand R*CO ₂ ^- . When a racemic mixture of Ag(O ₂ CR*) was used only the enantiomers (R,R)- and (S,S)-BiR ₃ (O ₂ CR*) ₂ were obtained.