This paper reports the electro- and photo-isomerization-induced isothermal phase separation of liquid crystals (LCs) and poly(N-vinylcarbazole) (PVK). The proposed phase separation process determines reformed PVK films on substrates to obtain switchable LC light valves. UV illumination induces simultaneous isothermal phase transition of the mixture and dissolution of PVK into the LCs. Phase separation of PVK and LCs occurs by the reversed phase transition via rapid electro-isomerization and slow dark-relaxation. During rapid phase separation, micron-sized LC domains (branch-like PVK structures) are generated to develop stable light scattering; during slow dark-relaxation, a uniform PVK film is obtained, thereby providing stable transparency.