This study systematically investigates the morphological appearance of azo-chiral dye-doped cholesteric liquid crystal (DDCLC)/polymer coaxial microfibers obtained through the coaxial electrospinning technique and examines, for the first time, their photocontrollable reflection characteristics. Experimental results show that the quasi-continuous electrospun microfibers can be successfully fabricated at a high polymer concentration of 17.5 wt% and an optimum ratio of 2 for the feeding rates of sheath to core materials at 25 °C and a high humidity of 50% ± 2% in the spinning chamber. Furthermore, the optical controllability of the reflective features for the electrospun fibers is studied in detail by changing the concentration of the azo-chiral dopant in the core material, the UV irradiation intensity, and the core diameter of the fibers. Relevant mechanisms are addressed to explain the optical-control behaviors of the DDCLC coaxial fibers. Considering the results, optically controllable DDCLC coaxial microfibers present potential applications in UV microsensors and wearable smart textiles or swabs.