Chitosan-poly(L-lactic acid-co-epsilon-caprolactone)(50:50) (P(LLA-CL)) (CS/P(LLA-CL)) blends were electrospun into nanofibers using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and trifluoroacetic acid (TFA) as solvents. Chitosan, which is difficult to electrospin into nanofibers, could be easily electrospun into nanofibers with addition of a small portion of P(LLA-CL). The fiber diameter depended on both the polymer concentration and the blend ratio of chitosan to P(LLA-CL). The average fiber diameter increased with increasing polymer concentration and decreasing the blend ratio of chitosan to P(LLA-CL). X-ray diffractometry (XRD) and Fourier-transform infrared (FT-IR) spectra were measured to characterize blended nanofibers. The porosity of CS/P(LLA-CL) nanofiber mats increased with increasing the weight ratio of chitosan to P(LLA-CL), while both the tensile strength and the ultimate strain increased with increasing P(LLA-CL) ratio. Fibroblast cell growth on nanofiber mats were investigated with MTT assay and scanning electron microscope (SEM) observation. The highest cell proliferation was observed on the nanofiber mats when the weight ratio of chitosan to P(LLA-CL) was 1:2. As SEM images shown, fibroblast cells showed a polygonal shape on blend nanofiber mats and migrated into the nanofiber mats.