In this study, a novel cation donor group 3-ethoxy-4-hydroxy benzaldehyde has been incorporated in the Stilbazolium cation with iodide anion to generate a new NLO activity of a single crystal of 4-(2-(3-ethoxy-4-hydroxy-phenyl)-vinyl)-1-methyl pyridinium iodide (MEMPI). The MEMPI crystal was effectively formed via the solvent evaporation technique. The structure and hydrogen bond interactions found in the molecule were determined by employing single-crystal X-ray diffraction. The compound crystallizes in the space group P21/c and monoclinic crystal pattern. The crystal structures are stabilized via intramolecular, intermolecular hydrogen bond interactions, C‒H···π, cation‒π, anion‒π, π···π stacking and lone pair-π interaction. In addition, a variety of O‒H···O, O‒H···I and C‒H···O interactions are also responsible for crystal packing. The 3D Hirshfeld surface and 2D fingerprint plots were used to examine the nature of intermolecular interaction. The 2D fingerprint maps indicate that the interactions between H···H contribute to 48.9 % of the total crystal stability. The newly synthesized material was characterized by 1H NMR and 13C NMR. In addition, the vibrational study of the synthesized molecule was performed using FTIR analysis. The grown crystal in linear optical characteristics were examined via a UV–Visible-NIR study. The photoluminescence (PL) activity of a MEMPI was studied with respect to the visible area and green colour emission was observed at 536 nm. The estimated CIE coordinates on the RGB colour gamut show the MEMPI crystal's ability to emit green light. The chemical etching approach was used to analyse the etch pit density and the growth habitat of the MEMPI crystal. The closed and open aperture Z-scan tests were carried out to determine the nature of third-order NLO susceptibility of the MEMPI crystal.