We report rhodium complexes bearing PAlP pincer ligands with an X-type aluminyl moiety. IR spectroscopy and single-crystal X-ray diffraction analysis of a carbonyl complex exhibit the considerable sigma-donating ability of the aluminyl ligand, whose Lewis acidity is confirmed through coordination of pyridine to the aluminum center. The X-type PAlP-Rh complexes catalyze C2-selective monoalkylation of pyridine with alkenes.