Single crystal of α-nickel sulphate hexahydrate, α-NiSO4. 6H2O (α-NSH) is grown from aqueous solution by slow evaporation method. Solubility and metastable zone width of α-NSH are determined from the aqueous solution. The three dimensional structure is elucidated by single crystal X-ray diffraction studies. The α-NSH crystallizes in the non – centrosymmetric tetragonal space group P41212. The relative contributions of various intermolecular interactions involved in the crystal structure are quantified using Hirshfeld surface analysis and the decomposed two dimensional fingerprint plots. Fourier transform infrared spectral analysis and Vickers microhardness studies are carried out to characterize the grown crystal. Further the grown crystals are characterized using TGA, DSC, UV–Vis–NIR and dielectric analysis. The third order nonlinear optical properties are studied by Z–scan technique with HeNe laser radiation of wavelength 632.8 nm and the corresponding nonlinear refractive index, absorption coefficient and optical susceptibility are calculated. Crystalline perfection is assessed by etching studies and laser damage threshold is observed for the grown crystal.