It is reported that a novel third order organic nonlinear optical material namely, Pyrrolidin-1-ium 2-chloro-4-nitrobenzoate 2-chloro-4-nitrobenzoic acid (PCNCN) has been synthesized and grown by isothermal solvent evaporation solution growth technique. Single crystal X-ray diffraction analysis revealed that PCNCN belonged to monoclinic crystal system with a centrosymmetric space group of P21/c. The morphology of the as grown PCNCN crystal compared well with that obtained by theoretically generated morphology. The molecular vibrations of PCNCN were analyzed through Fourier transform infrared and NMR spectrum analyses. Optical properties such as transmittance, photoluminescence, and laser damage threshold were studied. The thermal stability of PCNCN was measured through TG-DTA measurement. The dielectric properties such as dielectric constant, dielectric loss, ac conductivity and activation energy of PCNCN single crystal were studied as a function of frequency at different temperatures. The PCNCN single crystals were further characterized for their third order nonlinear optical properties such as nonlinear absorption coefficient, nonlinear refractive index and optical limiting behavior using continuous wave Nd: YAG laser. The quantum chemical investigations were performed using B3LYP/6-311++G(d, p) basis set. © 2019 Elsevier Ltd