Six compounds of cyclic hypervalent organobismuth(III) chlorides and triphenylgermylpropionates bearing a nitrogen or sulfur atom as intramolecular coordination atom have been synthesized and characterized. The results of single-crystal X-ray analysis reveal that the eight-membered tetrahydroazabismocine rings are highly flexible. The Bi–S or Bi–N bond lengths in the thiabismocine or azabismocine derivatives are dependent on how the substituted groups are acting on the Bi, S or N atom. The replacement of the chlorine atom in azabismocine and thiabismocine with the triphenylgermylpropionic group (Ph 3 GeCH 2 CH 2 COO) leads to the lengthening of Bi–N and Bi–S bond. The substituents connected with the nitrogen atom also have an effect on the Bi–N bond length of azabismocine. For example, a cyclohexyl group has electron-donating ability higher than a phenyl group; the replacement of the former by the latter would lead to the decline of Bi–N bond length and increase of C Ar –Bi–C Ar angle in the eight-membered ring. The in vitro antiproliferative activities of the fabricated materials were compared on gastric carcinoma cells by means of the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl tetrazolium bromide (MTT) method. It was found that the compounds show antiproliferative activity on gastric carcinoma cells (MGC-803) much higher than that of cisplatin. Moreover, there is enhancement of antiproliferative activity when the chlorine atom of the bismocine compounds is replaced by the triphenylgermylpropionic group, giving a low IC 50 value of 0.7μM for thiabismocine triphenylgermylpropionate.