This paper elucidates the means to control precisely the morphology of electrospun liquid crystal/polymer fibers formed by phase separation. The relative humidity, solution parameters (concentration, solvent), and the process parameter (feed rate) were varied systematically. We show that the morphology of the phase-separated liquid crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads-on-a-string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liquid-crystal (LC) core. The width of the polymer sheath and the diameter of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liquid crystals and because of their large surface area, they have potential applications as thermo-, chemo-, and biosensors. Because the size and shape of the liquid-crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphology will be crucial in developing these applications.