Oxidation of N,N‐bis(diphenylphosphanyl)naphthalen‐1‐amine (1) with elemental sulfur or gray selenium (1:1 molar ratio) gave the corresponding monosulfide and monoselenide bis(phosphanyl)amine ligands C10H7‐1‐N(P(E)Ph2)(PPh2) [E = S (2), Se (3)], respectively. Reactions of 2 and 3 with MCl2(cod) (M = Pd, Pt) afforded [MCl2{2‐κ2P,S}] [M = Pd(4), Pt(5)] and [MCl2{3‐κ2P,Se}] [M = Pd(6), Pt(7)], respectively. In contrast, reactions of the same ligands with NiCl2(PPh3)2 resulted in deselenization and desulfurization, producing complex 8 with the formula [NiCl2{1‐κ2P,P}]. Ligands 2 and 3, as well as their complexes 4–7 and 8 were identified and characterized by multinuclear NMR (1H, 13C, 31P, and 77Se NMR) spectroscopy, elemental analysis, and IR spectroscopy. Additionally, the molecular structure of 8 was obtained.