A series of poly(E >-caprolactone) (PCL)/cellulose acetate (CA) ultrafine fiber webs were prepared via electrospinning followed by deacetylation in an aqueous alkaline solution to convert CA into cellulose (CEL). The wetting properties of PCL/CA and PCL/CEL blends were evaluated to investigate wicking behavior. The results showed that the conversion of PCL/CA into PCL/CEL leads to an improved wettability. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) study revealed that CA was completely converted into CEL after deacetylation, and PCL/CEL blends exhibited characteristics peaks of both constituent fibers. The differential scanning calorimetry (DSC) analysis demonstrated that the PCL/CA ultrafine fibers were partially miscible in PCL/CA ultrafine fibers. The fiber morphology under field emission scanning electron microscopy (FE-SEM) showed that the electrospun ultrafine fibers were bead free. The crystallinity of PCL-CEL, (1:4) blend was greatly decreased in comparison to the treated PCL as revealed by wide angle X-ray diffraction (WAXD) measurements. The potential applications of PCL/CEL webs include liquid biofilters, biosensor and biomedical materials.