The asymmetric unit of the title compound, C(10)H(8)·2C(16)H(14)N(4), consists of one mol-ecule of N,N'-bis-(pyridin-2-yl)benzene-1,4-diamine (PDAB) and one half of the centrosymmetric naphthalene mol-ecule. The PDAB mol-ecule adopts a non-planar conformation with an E configuration at the two partially double exo C N bonds of the 2-pyridyl-amine units. In the crystal, N-H⋯N hydrogen bonds between the PDAB mol-ecules generate a cyclic R(2) (2)(8) motif, leading to the formation of PDAB tapes extending along [100]. The tapes are arranged into (010) layers and the naphthalene mol-ecules are enclosed in cavities formed between the PDAB layers.