As a high-performance polymer, carboxylic-functionalized poly(arylene ether ketone)s (PCA-PAEK) was electrospun into ultrafine fibers and characterized. To optimize the process, a set of experiments were designed. As a result, the optimum condition was obtained and the polymer concentration was determined as the most important factor. Incidentally, the PCA-PAEK fibers were found to exhibit superabsorbent behavior. In order to investigate processing characteristics, PCA-PAEK fibers fabricated from different solution concentrations were employed and characterized. The results showed that porosity and changes in water contact angle and water absorbency decreased with an increase in concentration. In addition to a high water absorption capacity, the fibers exhibited good water retention and repeated water absorbency as well. The study on kinetics of water absorption and swelling behavior showed that the mechanism was dependent on the polymer concentration from which the fibers were electrospun. Moreover, both dry and wet PCA-PAEK fibers showed high mechanical properties. Due to these properties, the PCA-PAEK ultrafine fibers are potentially useful as a water-absorbent material.