<p>For the first time, hydrogen bond-rich organic multi-component hydrous salt cocrystal tetrakis (2,4,6-triaminopyrimidinium) tetrakis (4-nitrophenolate) 4-nitrophenol pentahydrate (ANNH) was effectively synthesized and grown into a single crystal using the slow evaporation method. The growth and dissolution rates are relatively higher along a direction, as predicted utilizing Bravais–Friedel–Donnay–Harker (BFDH) morphology. ANNH was crystallized in centrosymmetric space group P1̅ of triclinic system. As determined by single-crystal XRD analysis, asymmetric unit of ANNH contains fourteen molecules stabilized through eighty-seven intermolecular hydrogen bonding interactions with nine symmetry equivalent positions are predicted. Hirshfeld surface, finger print analysis, shape index, and curvedness are carried out to investigate the C–H…O, C–H…N, N–H…N, N–H…O, O–H…O, O–H…N, C–H…π and π–π interactions. The minimal percentage of porosity has been found by void analysis. Crystalline purity is confirmed by comparison of experimental PXRD with the simulated one. Raman and FTIR studies are effectively performed to investigate the vibrational modes of different functional groups. The high cut-off wavelength 400&#xa0;nm is found that by UV–Visible absorbance spectroscopy. A high-intensity green light emission centered at 467&#xa0;nm was observed from ANNH in photoluminescence investigation. Thermal stability of ANNH up to 168 ℃ was further assessed through thermo-gravimetric and differential thermal analysis. The Z-scan technique, using a 632.8-nm continuous wave laser, was employed to investigate the third-order nonlinear optical characteristics of the synthesized ANNH crystal, including nonlinear refractive index (<i>n</i>_<i>2</i>), absorption coefficient (<i>β</i>) and third-order susceptibility (<i>χ</i>^<i>3</i>).</p>