A series of novel 4f-3d crystalline porphyrinic compounds, {[Co(TPPS)] 2 [Ln(Histidine) 5,10,15,20-tetra(4-sulfonatophenyl)porphyrinato) with TPPS and histidine as mixed ligands, have been prepared and characterized by single-crystal X-ray diffraction technique. Complexes 1−3 are isomorphous and characteristic of a threedimensional (3D) framework with the lanthanide ions in two kinds of coordination geometries, i.e., eightfold square antiprism and ninefold monocapped square antiprism. The porphyrin macrocycles adopt a saddle-distorted nonplanar conformation with an embedded cobalt ion binding to four pyrrole nitrogen atoms. As revealed by the photoluminescence measurement, they exhibit blue emission. Variable-temperature magnetic susceptibility reveals that complexes 1−3 are antiferromagnetic. Their FTIR, CV, DPV, and UV/vis results are also studied in detail.