Polydentate NPPN ligands containing nitrogen and chiral phosphorus atoms have been synthesized (A−D), starting from diphosphines (dppe and dppp) and 2-(3‘,4‘-dihydro-4‘-R-2‘-oxazolyl)-1-chlorobenzene (R = ethyl, isopropyl). Their coordination behavior has been studied with nickel and palladium precursors, giving mono- and bimetallic complexes depending on the reaction conditions. For the monometallic compounds, the NPPN ligands act as tetra- or tricoordinate groups (Ni-a−d and Pd-a,b, respectively), while for the bimetallic palladium complexes, the ligand bridges two metallic atoms (1a, 3a−c, 4a−c, 5a−c, 6a−d, 7a, 8d) in an N,P bis-bidentate coordination. The X-ray crystal structure of bis(η3-2-methylallyl)[μ-(4‘R)-phenyl(2-(3‘,4‘-dihydro-4‘-ethyl-2‘-oxazolyl))phenylphosphinoethane]dipalladium(II) hexafluorophosphate (RSRR-7a) is described. Acyl complexes 4a−c were obtained from the methyl compounds 3a−c by insertion of carbon monoxide into Pd−CH3 bond, at high pressure and room temperature. However, these compounds did not undergo insertion of norbornene or norbornadiene into the Pd−COCH3 bonds. Ionic methyl complexes 5a−c reacted faster than the neutral 3a−c toward the insertion of CO, but these ionic acetyl compounds decarbonylated easily, even in the solid state. The activity of the allylic complexes (6a−d) in palladium-catalyzed allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate was tested, affording enantiomeric excesses up to 90%. The enantioselectivity of these catalytic systems exhibits a strong dependence on the Pd/NPPN ratio, because of the presence of different coordination modes.