A nonlinear optical (NLO) sodium 4-methyl-3-nitrobenzoate monohydrate (Na4M3N) single crystal was synthesized and grown by the slow cooling solution growth method using an ethanol-water (1:1) mixed solvent. Powder X-ray diffraction (PXRD) reveals the crystallinity of Na4M3N compound. The Na4M3N crystal was estimated with a single crystal XRD instrument and it was identified to be in the centrosymmetric space group (P21/c) having a monoclinic system. The vibrational, proton (1H) and carbon (13C) NMR spectral analysis substantiates the functional groups, hydrogen and carbons in the synthesized compound. The Hirshfeld surfaces analysis was executed to know the different type of interactions present in the crystal. From the UV–vis spectrum, the optical band gap and cut-off wavelength of the Na4M3N crystal are endowed to be 5.06 eV and 254 nm respectively. The Na4M3N crystal was subjected to a thermogravimetric as well as differential thermal analysis for discerning the thermal characteristics. The LDT value of crystal was endowed to be 5.8 GW/cm2 using Nd: YAG laser and the value is superior to that of KDP and Urea. The emission region of the compound was identified by the photoluminescence emission spectrum. The crystalline quality was again confirmed by lifetime measurements. The thermo-optic coefficient (dn/dt) was determined to be –3.5 × 10−5 K−1. The reverse saturable absorption observed by third-order NLO studies dictates the suitability for optical limiting applications. Vickers microhardness test showed that Na4M3N crystal was a soft material. The average etch pit density (3.2 × 103 cm−2) was determined from chemical etching studies. The complex dielectric constant, electric modulus and electrical conductivity values were measured as a function of frequency to get information on the conduction mechanisms. © 2019 The Physical Society of the Republic of China (Taiwan)