Perovskite Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) is a promising mixed-conducting ceramic membrane material in addition to being a good electrode catalyst for solid oxide fuel cells. In this study, BSCF powder was synthesized via a chelated water-soluble complex method at relatively low temperatures. The combined ethylenediaminetetraacetic acid and citric acid was used for the synthesis of a complex-based precursor, followed by thermal decomposition of the precursor at high temperatures. Thermal behavior, crystal phases, and structures of the prepared powders were characterized by thermogravimetric analysis/differential scanning calorimetry, XRD, and scanning electron microscopic (SEM) techniques, respectively. Pure and single-phase perovskite could be obtained after sintering at a temperature higher than 800°C for 5 h. The soft precursor powder synthesized at lower temperatures, i.e., 600°C, is water insoluble and more appropriate for use as a membrane material to prepare gas-tight tubular or hollow fiber ceramic membranes. By contrast, the hollow fibers prepared via the traditional techniques where the perovskite powder is used as the starting membrane materials display gas leakage. The fibers were characterized by SEM, XRD, and tested for air separation at ambient pressure and temperatures between 700° and 950°C. The oxygen flux measured in this work reached 3.90 mL·(min·cm2)−1 and compares favorably with any experimental values reported in the open literature.