The preparation, spectroscopic characterization (NMR and IR spectroscopy), and solid‐state structures of tri(3‐pyridyl)‐ and tri(4‐pyridyl)phosphine chalcogenides (E = O, S, Se) as well as their ability to behave as ligands for ZnTPP (TPP = tetraphenylporphyrinate) moieties are reported. In the solid state, the compounds from this family are three‐bladed molecular propellers that crystallize as racemates. Both triorganophosphine sulfides and selenides, (3‐Py)3PE [Py = pyridyl, NC5H4; E = S (2), Se (3)] and (4‐Py)3PE [E = S (6), Se (7)], quantitatively form complexes with ZnTPP by selective coordination of all three pyridyl groups of a molecular unit to three metalloporphyrin moieties. The formation of these complexes in chlorinated solvents is unambiguously proven by spectroscopic methods (i.e., multinuclear NMR and UV/Vis spectroscopy). The affinity of these ligands towards ZnTPP is different in benzene, yielding a mixture of products in solution.