A new organic stilbazolium derivative crystal 2-[2-(3-hydroxy-4-methoxy-phenyl)-vinyl]-1-methyl-pyridinium naphthalene-2-sulfonate dehydrate (C₂₅H₂₃NO₅S·2H₂O) (VSNS) was synthesized successfully. Single crystals were grown in a mixed solvent of methanol–acetonitrile (1 : 1) using a slow evaporation method at room temperature. Solubility of the synthesized VSNS material was experimentally determined for various temperatures using a methanol–acetonitrile mixed solvent. A single crystal X-ray diffraction study confirmed the crystal structure and morphology of VSNS. The crystalline nature of the title material was analyzed by powder X-ray diffraction analysis, and the presence of expected functional groups and the molecular structure of VSNS was identified by FT-IR and ¹H NMR spectroscopic studies. Optical absorption was recorded using UV-Vis-NIR spectral analysis, and linear optical constants such as the absorption coefficient, band gap, extinction coefficient, refractive index and reflectance were calculated. The luminescence property of the crystal grown showed green emission radiation. The thermal stability of the crystal was analyzed by TG–DTA studies, and the hardness, Meyer index, yield strength, and elastic stiffness constant were estimated using a Vickers microhardness tester. Layer growth pattern was observed in chemical etching studies using a Carl Zeiss optical microscope at 50× magnification. Laser damage threshold energy was measured using an Nd:YAG laser (1064 nm). Variation of the dielectric response of the grown crystal was studied at room temperature. The third-order nonlinear optical property of VSNS was investigated in detail using a Z-scan technique with He–Ne laser at 632.8 nm. The second-order molecular hyperpolarizability γ of the crystal grown was 7.986 × 10⁻³⁴ esu. This encouraging result of the Z-scan studies suggests that the VSNS crystal is a candidate material for photonics devices, optical switches, and optical power limiting applications.