In this study, the optical nonlinearity of LCs with cell substrates coated with gold-nanoparticle (AuNP) -doped PVA alignment layers were examined using the Z-scan technique. The results show that the nonlinear refractive index n2 of the sample is enhanced by the gold nanoparticles doped in the alignment layers, because of the thermal effect of the absorption by the surface of the sample through the localized surface plasmon resonance (LSPR) of the gold nanoparticles. As the concentration of AuNPs in the alignment layers of the LC sample increases, the thermal effect of the LSPR increases, and |n2| observably increases. Furthermore, the self-defocusing effect (n2<0) of the sample can be modulated by the application of an external voltage, and a self-focusing effect (n2<0) can be observed when samples are illuminated by a high-intensity laser with the application of a high voltage. Therefore, the magnitude and the sign of n2 of the sample can be modulated by combining the applied electric field and the optical field.