Macroscopic fibers with superior mechanical performance can be prepared by spinning process using anisotropic and highly oriented liquid crystal spinning dope instead of traditional one. This makes it possible to prepare fibers made from novel materials like graphene, carbon nanotube, and so on. Functional organicinorganic hybrid fibers have been designed and synthesized for application in various areas on the basis of hybridization of organic materials and inorganic materials. Organicinorganic hybrid fibers have great potential in assembling flexible supercapacitors. In this paper, basic knowledge of liquid crystal spinning technology was introduced firstly. Secondly, recent advances in the synthesis of macroscopic fibers assembled from organic and inorganic liquid crystals, particularly organicinorganic hybrid fibers spun from liquid crystals, were demonstrated. Thirdly, recent researches of flexible supercapacitors fabricated with aforementioned hybrid fibers as fibrous electrodes were summarized. Finally, problems and future developments in the fields of liquid crystal spinning and fibrous flexible supercapacitors were discussed.