A process for making a stimuli responsive liquid crystal-polymer composite fiber comprising mixing a liquid crystal, a polymer, and a solvent; processing the mixture in the presence of an electric potential across a collection distance; phase separating a polymer and said liquid crystal; and encapsulating said liquid crystal within said polymer. The fiber generally comprises a liquid crystal core and a polymer shell wherein the liquid crystal is responsive to chemical changes, thermal and mechanical effects, as well as electrical and magnetic fields. A liquid crystal containing fiber can be utilized as optical fibers, in textiles, and in optoelectronic devices.