The title compound cyclohexylbis(2-pyridyl)phosphane (1) was synthesized by a Pd0-catalyzed cross-coupling reaction from 2-bromopyridine and cyclohexylphosphane in 98% yield. Compound 1 formed colorless crystals that were moderately air-stable. It reacted, in CH3CN, with CuOTf (OTf = OSO2CF3), AgBF4, and Co(BF4)2 to form the complexes [Cu2{CyP(2-Py)2}2(NCCH3)2](OTf)2 (2), [Ag2{CyP(2-Py)2}2(NCCH3)2](BF4)2 (3), and [Co2{CyP(2-Py)2}2(NCCH3)2](BF4)4 (4), respectively. In these complexes, the pyridylphosphane ligands coordinate to two metal centers in a head-to-tail fashion involving both the P and the N atoms simultaneously. The compounds represent the first structurally characterized examples of dimeric dinuclear pyridylphosphane complexes showing the P,N,N′ coordination. Reactions of 1 with other salts containing Cu+1 and Co+2 centers and coordinating anions resulted in different coordination modes. Thus, CuI reacted with 1 to form the complex [Cu2{CyP(2-Py)2}2I2] (5) with both coordinated P and N donor centers and a terminal iodide. In contrast, the reaction of 1 with CoCl2 afforded the mononuclear complex [Co{CyP(2-Py)2}Cl2}] (6) in which only the pyridyl N atoms and the chlorine ligands were coordinated to the metal center. X-ray analyses of the compounds 1, 2, 3, 5, and 6 are reported.