<p>The linear optical properties, nonlinear optical properties, and reactivity of various phenols were studied, calculated, and analyzed in detail using quantum chemical calculations. Linear (dipole moment, mean polarizability, polarizability anisotropy) and nonlinear optical properties (total first hyperpolarizability, electric-field-induced second harmonic generation, hyper-Rayleigh scattering hyperpolarizability, and the depolarization ratio) were computed by employing five DFT functionals (B3LYP, PBE0, CAM-B3LYP, ωB97X-D, and M05-2X) in conjunction with the 6­311+G** basis set. The differences in (hyper)polarizability as a consequence of phenol structures were consistent among functionals, facilitating the deduction of structure–property relationships. Among the selected phenols, eugenol showed the maximum mean polarizability and polarizability anisotropy of 132.66 and 74.54 a.u., respectively. The <i>β</i>_// amplitude was ~ 1.5 to 11 times more than other phenols. A high total first hyperpolarizability <i>β</i>_tot up to 640.37 a.u. and a low energy gap Δε less than 3.69&#xa0;eV were obtained. The <i>β</i>_tot amplitude of eugenol is nearly 15 times higher than that reported for urea and almost five times higher than that reported for <i>p</i>-nitroaniline. Hence, we believe that the current investigation would further interest researchers in exploring these phenols in nonlinear optical (NLO) materials.</p> Graphical Abstract <p></p>