Caffeic acid (CA) was chemically immobilized onto the surfaces of the individual electrospun poly(L-lactic acid) (PLLA) fibers to enhance the hydrophilicity and impart the antioxidant activity to the obtained fibrous membranes. This was done in two sequential steps. First, amino groups were covalently introduced onto the surfaces through the reaction with 1,6-hexamethylenediamine (HMD). In the second step, the amino moieties reacted with CA, which had been preactivated sequentially with 1 -ethy1-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). The success of the reactions was confirmed by the ninhydrin assay and X-ray photoelectron spectroscopic analysis (XPS). Indirect cytotoxicity evaluation with murine dermal fibroblasts (L929) and human dermal fibroblasts (HDFa) revealed that the neat and the modified PLLA fibrous matrices released no substances in the levels that were harmful to the cells. Direct culturing of HDFa on these fibrous substrates indicated that they supported the proliferation of the cells on days 2 and 3 very well and that the CA-immobilized substrates exhibited the highest cell viability. Lastly, the antioxidant activity of the CA-immobilized substrates, as revealed by the 1,1-dipheny1-2-picryldrazyl (DPPH) radical scavenging assay, was as high as 88% on average.