To provide an insight into the microscopic third-order nonlinear optical (NLO) behavior of a series of azo-azulenes; both dispersion-free (static) and also frequency-dependent (dynamic) linear polarizabilities (α) and second hyperpolarizabilities (γ) at 532nm wavelength have been theoretically investigated by means of a time-dependent Hartree-Fock (TDHF) method. The maximum one-photon absorption (OPA) wavelengths recorded by quantum mechanical computations using a configuration interaction (CI) method are estimated in the visible region, supporting the π→π* transitions. The ab-initio calculation results with non-zero values on (hyper)polarizabilities indicate that the title compounds might possess microscopic third-order NLO phenomena. © 2012 Photonics Society of Poland.