Five crystalline molecular complexes of phenazine (phz) with N,N-bis(2-pyridyl)aryldiamines and N,N′-diphenyl-1,4-diaminobenzene of different stoichiometries were prepared and their structures were studied by X-ray crystallography. The observed crystal packing results from concerted action of the N–H⋯N hydrogen bonds, π–π stacking of the phz units and edge-to-face interactions between the aromatic rings of the component molecules. The planar Z conformation adopted by the N-aryl-2-aminopyridine moieties facilitates their interaction with the phz system.