The reaction of [Fe3(CO)12] with diphenyl-2-pyridylphosphine (PPh2Py) in refluxing toluene for 1 h afforded three compounds, [Fe2(CO)6(μ-PPh2)(μ-κ2-C,N-C5H4N)] (1), [Fe(CO)4(κ1-P-PPh2Py)] (2), and [Fe(CO)3(κ1-P-PPh2Py)2] (3) in 23%, 10% and 3.5% yields after work-up, respectively. The PPh2Py ligand acts as a terminal P-donor ligand in 2 and 3, while in 1 it underwent a selective phosphorus–carbon(pyridyl) bond cleavage to afford phosphido- and pyridyl-bridged ligands. The complexes were characterized by elemental analysis, FAB-mass, FTIR, 1H and 31P–{1H}NMR spectroscopies. Compounds 1 and 2 were also characterized by X-ray single crystal.