The study uses nematic liquid crystal doped with 12-hydroxysteric acid (HSA) to make liquid crystal cell and observe its characteristics. We found that when doping HSA into nematic liquid crystal and when without any alignment treatment on the glass substrate, HSA has spontaneous vertical arrangement phenomenon on liquid crystal. It avoids the procedures for general vertical alignment which must make surface treatment on the substrate and can further simplify the process. Then, we made the HSA and liquid crystal sample with only one side parallel alignment. This sample not only shows the same initial phase as hybrid alignment liquid crystal sample, but also has multistable operation mode depending on HSA’s self-organized characteristic.