Double-bridged cofacial Ni porphyrin dimers 2 with 2,2'-bipyridyl pillars were effectively prepared by a one-step reductive homocoupling reaction of bis(chloropyridyl)-substituted Ni porphyrin derivatives followed by a specific separation of a cyanopropyl-modified silica gel column using pyridine eluent systems. The structural analyses of 2 and its Pd complex were carried out in their solid and solution states by means of X-ray single crystal analysis and NMR, respectively. The complexation of η 3 -allylpalladium chloride ( Pd ) with 2 on the spatially restricted 2,2-bipyridine moieties on 2 gave a 2:1 ( Pd : 2 ) complex, in which the 2,2'-bipyridine ligands only provided one of the N atoms on a 2,2'-bipyridine ligand to a Pd . Therefore, the 2,2-bipyridine moieties acted as a monodentate ligand.