The present study reports that isothermal phase transition induced by photoisomerization of azobenzene liquid crystals (azo-LCs) from transto cis-isomers results in the dissolution of poly(N-vinylcarbazole) (PVK) into azo-LCs. Transparent (scattering) states can be demonstrated using uniform (rough) morphologies of PVK generated by slow (rapid) phase separation of PVK and azo-LCs from cis- to trans-isomers. The PVK films were examined in detail using scanning electron microscopy. Scattering performance resulting from the rough PVK surface induced micron-sized LC domains, and transparent performance resulting from the reformed uniform PVK surface can be optically and reversibly switched. Finally, all-optically controllable and highly efficient (contrast ratio of 370:1) scattering mode light modulators based on azo-LCs and PVK films were demonstrated.