||Polyimide has the mechanically and thermally stable property and strong anchoring interactions with the LC molecules have been widely used. LC molecules (abbreviated as CAn-OH) were specifically designed for the automatic vertical alignment (VA) layer of nematic liquid crystal (LC), which can be applied for the fabrication of remote-controllable devices. The CA1-OH giant surfactant in the nematic medium gradually diffused onto the substrate of LC cell and self-assembled to the expanded monolayer structure, which can construct the VA layer without forming the macroscopic aggregations. The CA3-OH compound forming the condensed monolayer structure exhibited a planar alignment (PA) rather than a VA. The reversible LC orientation was demonstrated by tuning the wavelength of light, which can allow us to fabricate the remote-controllable and photopatternable LC optical devices. This work was supported by BK21 Plus program, the BRL 2015042417, Mid-Career Researcher Program (2016R1A2B2011041).