Paracetamol-Picric acid (PP) cocrystals were grown from ethanol by slow evaporation solution growth technique. The compound C14H12N4O9 crystallizes in monoclinic system with centrosymmetric space group P21/c. The band gap energy was estimated by the application of Kubelka–Munk algorithm and the cut-off wavelength is ∼491 nm. The molecule is associated with accommodating weak C[sbnd]H⋯O, O[sbnd]H⋯O, π … π and H⋯H stacking interactions, very much responsible for the formation and strengthening of supramolecular assembly. Inter- and intramolecular hydrogen bonding interactions show supramolecular architecture in the crystal packing. Third-order nonlinear optical properties of the grown crystal were derived by employing a single beam Z-scan technique at a wavelength of 532 nm diode pumped CW Nd:YAG Laser system. Theoretical calculations were performed using density functional theory (DFT) method to derive the optimized geometry, dipole moment, polarizability and hyperpolarizability. Molecular interactions are analyzed and quantified by Hirshfeld surfaces, derived from single crystal XRD data. Fingerprint plots of Hirshfeld surfaces were used to locate and analyze the percentage of hydrogen bonding interactions. The O⋯H/H⋯O interactions mainly contribute to the observed microlevel nonlinearity. © 2019