We report the synthesis of a novel porphyrin-based metal carboxylate framework, [Cu-2(ZnBBCPPP)(H2O)(2)]center dot 6DMF center dot 11H(2)O (BBCPP-Cu-2), with a large void volume, by using a two-dimensionally expanded building block: {bis[3,5-bis(4-carboxyphenyl)phenyl]porphyrinato}zinc (ZnBBCPPP). Singlecrystal X-ray analysis of BBCPP-Cu-2 revealed a threedimensional network. The void volume per unit cell of BBCPP-Cu-2 is 76.8%, which is considerably larger than that of previously reported porphyrin-based MOFs.