A ferrocene-based phosphinopyridine, Ph2PfcPy (1; fc = ferrocene-1,1′-diyl, Py = 2-pyridyl), was newly synthesized by Negishi coupling of Ph2PfcZnCl with PyBr. Its homologous compound Ph2PfcCH2Py (2) was obtained by reductive dehydroxylation of Ph2PfcCH(OH)Py (4), the latter resulting via reaction of in situ generated Ph2PfcLi with PyCHO. Depending on the stoichiometry, compounds 1 and 2 react with [PdCl2(cod)] (cod = η2:η2-cycloocta-1,5-diene) to give P,N-chelate and bis-phosphine complexes, [PdCl2(L-κ2P,N)] (5, L = 1; 6, L = 2) and [PdCl2(L-κP)2] (7, L = 1; 8, L = 2), respectively. Analogously, [(LNC)PdCl]2 or [(LNC)Pd(MeCN)2]ClO4 (LNC = [(2-dimethylamino-κN)methyl]phenyl-κC1) react with 1 and 2 to afford complexes featuring these compounds as P-monodentate ligands ([(LNC)PdCl(L-κP)]: 9, L = 1; 10, L = 2) or P,N-chelating donors ([(LNC)Pd(L-κ2P,N)]ClO4: 11, L = 1; 12, L = 2), respectively. With the exception of compound 9, which undergoes self-ionization in solution, all complexes are defined air-stable...