A wheel-like dodecanuclear cobalt(II) cluster complex [Co12(TBSOC)4(5-NH2-tz)8(CH3OH)6]·3H2O·5CH3OH (1, 5-NH2-tzH = 5-amino-1H-tetrazole) and an irregular rod-like tetradecanuclear cobalt(II) cluster complex [Co14(OH)2(TBSOC)4(5-ph-tz)10(5-ph-tzH)2(CH3OH)2]·16·5H2O·2CH3OH(2, 5-ph-tzH = 5-phenyl-1H-tetrazole) were solvothermally synthesized by using p-tert-butylsulfonylcalix[4]arene (H4TBSOC) and 5-subst-1H-tetrazoles as ligands. Single-crystal X-ray diffraction analyses revealed that the 5-substituent groups of the 1H-tetrazole bridging ligands have asignificant influence on the structure of the polynuclear cobalt(II) cluster complexes: 1 shows a closed wheel-like structure whereas 2 an open rod-like structure. A magnetic investigation indicated that both complexes exhibit antiferromagnetic properties.