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Pure and o-nitroaniline (O-NA) doped benzil single crystals were grown by the slow cooling solution growth method. The doping of O-NA is associated with the strong interaction between the guest and host molecules by the hydrogen bonding. Incorporation of O-NA in the lattice enhances the crystallinity. The nonlinearity increases due to the inductive nitro group added to the benzil. The values of nonlinear absorption coefficient (β) and nonlinear refractive index (n 2) of benzil are −78 × 10−3 cm/W and −22 × 10−3 cm/W, while the corresponding values for O-NA doped benzil are −9.4 × 10−9 and −6 × 10−7 cm2/W, respectively. The figure of merit values of benzil and O-NA doped benzil are 2265 and 4990, respectively. The increase in hardness on doping of O-NA to benzil is due to the strong hydrogen bond.