Liquid crystals decorated gold nanoparticles are synthesized as the molecular architecture consists of the azobenzenes moieties with alkene as the peripheral units, which are connected to gold nanoparticles (Au-NPs) via thiolated phenolic units are in the middle. The morphology and mesomorphic properties were investigated by the field emission scanning electron microscope, high-resolution transmission electron microscopy, differential scanning calorimetry, and polarizing optical microscopy. The aromatic thiolated azobenzene moieties with gold nanoparticles showed smectic A phase with monotropic nature only appeared in the cooling cycle. HR-TEM measurement showed that the functionalized Au-NPs are well dispersed without any aggregation. However, the absorption spectrum of peripheral azobenzene units shows strong absorption maxima in the ultraviolet region at 378 nm due to π-π* transition. For n-π* transition, a weak absorption band is observed in the visible region at 472 nm. The photo-isomerization characteristic is measured using absorption spectroscopy. The photosaturation of Au-NPs is found at the time duration of 16 s. The thermal back relaxation is completed after the time interval of 70 min. Moreover, Au-NPs showed excellent stability towards photo-decay. Therefore, Au-NPs compound is suitable in the field of optical storage and molecular switching.