We describe here the preparation of poly(caprolactone) (PCL)-chitin nanofibrous mats by electrospinning from a blended solution of PCL and chitin dissolved in a cosolvent, 1,1,1,3,3,3-hexafluoro-2-propanol and trifluoroacetic acid. Scanning electron microscopy showed that the neutralized PCL-chitin nanofibrous mats were morphologically stable, with a mean diameter of 340.5 +/- 2.6 nm, compared with a diameter of 524.2 +/- 12.1 nm for PCL mats. The nanofibrous mats showed decreased water contact angles as the proportion of chitin increased. However, the tensile properties of nanofibrous mats containing 30 similar to 50% (wt/wt) chitin were enhanced compared with PCL-only mats. In vitro studies showed that the viability of human dermal fibroblasts (HDFs) for up to 7 days in culture was higher on composite (OD value: 1.42 +/- 0.09) than on PCL-only (0.51 +/- 0.14) nanofibrous mats, with viability correlated with chitin concentration. Together, our results suggest that PCL-chitin nanofibrous mats can be used as an implantable substrate to modulate HDF viability in tissue engineering.