AbstractA simple direct condensation of 2,6‐bis(phenylamino)pyridine (1) and ClPPh2 under basic conditions allowed straightforward synthesis of the new multidentate Ph2P‐substituted anilido‐pyridine proligands 2 a and 2 b. Proligand 2 a was used in σ‐bond metathesis reactions with Me3Al affording either dinuclear product 3 a‐Al2 or mononuclear 4 a‐Al, depending on the reaction conditions. These complexes were authenticated by X‐ray crystallography, NMR spectroscopy and microanalysis. The analysis of the interaction between Me2Al and Ph2P fragments in 4 a‐Al was performed by structural and computational studies. The reactivity of 4 a‐Al was preliminary assessed in several representative reactions.