A method to control on-demand phase transition and alignment of organic–inorganic hybrid containing lyotropic liquid crystals (LLCs) have been developed. By using polysiloxane containing hygroscopicity and photocrosslinking groups, the phase transition of the LLCs can be induced by changes in humidity. The phase-transition behavior of the LLCs in polysiloxane can be suppressed by light irradiation. Further, the author proposed new methods for vertically aligning nanochannels by using surface interaction or the spontaneous vertical-aligned nature, and photopatterning of chromonic dye aggregates.