A new noncentrosymmetric organic cocrystal, 4-cyanopyridine·2,4-dinitrophenol (4CPDNP), was synthesized via slow evaporation and characterized using spectroscopic, structural, optical, dielectric, and surface analyses. FT-IR, FT-Raman, and NMR confirmed the coexistence of functional groups from both coformers and strong intermolecular hydrogen bonding. UV-DRS revealed a red-shifted absorption edge with a reduced band gap (2.68 eV), while photoluminescence showed strong green emission at 516 nm, indicating efficient intramolecular charge-transfer transitions. SEM-EDS confirmed crystalline morphology and elemental purity. Thermal analysis demonstrated stability up to ∼112 °C, with complete decomposition by 285 °C. Dielectric studies indicated frequency- and temperature-dependent polarization behavior, while AC conductivity followed a thermally activated hopping mechanism. Powder SHG measurements showed 4CPDNP exhibits 1.97x the efficiency of KDP, attributed to its orthorhombic P212121 symmetry and donor-acceptor π-conjugation. PXRD confirmed phase purity, and SCXRD revealed a robust hydrogen-bonded supramolecular network. Hirshfeld surface and fingerprint analyses highlighted dominant H O (28.1 %) and H N (11.7 %) interactions. The results demonstrate that 4CPDNP is a promising NLO-active material with desirable optical transparency, thermal robustness, and efficient second-order response for photonic and optoelectronic applications. © 2025 Elsevier B.V.