A new molecular adduct namely, 4-(dimethylamino)benzaldehyde 4-nitrophenol (4DMAB4NP), has been synthesized through crystal engineering route by reacting 4-(dimethylamino)benzaldehyde and 4-nitrophenol in equimolar ratio. This hydrogen bonded material is found to have crystallized with centrosymmetric space group of P21/c at room temperature (RT) and making it appropriate for third order nonlinear optical (TONLO) applications. The different kinds of functional groups existing in the 4DMAB4NP were recorded and assigned through FTIR and NMR spectral studies. Thermal behavior of 4DMAB4NP was analyzed through TGA and DTA analyses. Its solubility in toluene solvent was measured to obtain high quality single crystals. The 4DMAB4NP single crystals were characterized for their laser damage threshold, TONLO properties and optical limiting behavior. Further, the dielectric behavior of 4DMAB4NP single crystal were also investigated as a function of temperature (313–343 K). In addition, density functional studies of 4DMAB4NP molecule in gaseous phase were accomplished at the B3LYP/6–311++G (d, p) basis function. Finally, 3-D Hirshfeld surface maps and the 2-D fingerprint diagram were generated for the title molecule by using crystal explorer 3.1 program. © 2018 Elsevier B.V.