Two novel calixarene-based compounds, {[Co 4 Cl(TC4A)(HCOO) 3 ] 2 (4,4′-bpy) 2 } (CIAC-206) and {[Co 3 (H 2 O)(SC4A-SO 2 )(HCOO) 2 ] 2 (4,4′-bpy)} n (CIAC-207) (H 4 TC4A=p-tert-butylthiacalix[4]arene, SC4A-SO 2 =p-tert-butylsulfonylcalix[4]arene, 4,4′-bpy=4,4′-bipyridyl) were synthesized under solvothermal conditions, and characterized by single crystal X-ray diffraction analysis, TG–DSC analysis, elemental analysis and IR spectroscopy. These two structures are featured with isolated Z-shaped Co 8 entities containing two Co 4 -TC4A subunits bridged by two parallel 4,4′-bpy (CIAC-206) and some zigzag chains with [Co 3 -SC4A-SO 2 ] 2 dimers bridged by single 4,4′-bpy (CIAC-207), respectively. In order to evaluate their properties, the N 2 sorption behavior and magnetic property were examined.