A porous metal–organic material of the doubly deprotonated form of a new bis(aroylhydrazone) ligand (L12−) was self-assembled from 2,3-butanedione, isonicotinoyl hydrazine and lead nitrate. X-ray single crystal analysis revealed that six L12− and six Pb2+ are arranged alternately to form a metallomacrocycle in the porous material. Weak coordination bonds together with π⋯π interactions connect the metallomacrocycle units rather strongly into two interpenetrating unique 3D networks. TG, PXRD and dehydration investigation showed that all of the coordination and guest water molecules in the material can be removed upon heating to give the activated structure with vacant pores and open Pb sites. The material can reversibly adsorb/desorb water and small alcohol molecules.