This study reports for the first time on the production of poly(epsilon-caprolactone)/chitosan blend fibers for future application as tissue engineering scaffolds. Fibers of chitosan and poly(epsilon-caprolactone) were prepared by wet spinning from blend solutions, using a formic acid/acetone 70:30vol.% mixture as common solvent and methanol as coagulant. By this method, blend fibers with a wide compositional range and controllable diameters could be produced. Scanning electron microscopy shows the existence of roughness and porosity at the micron level scale in the blend fiber surface that could be potentially advantageous for cell attachment. Studies were also conducted using both conventional and innovative techniques to evaluate compatibility between the polymers, including FTIR imaging and investigation of the glass transition of chitosan using dynamic mechanical analysis on samples with controlled swelling. The data suggest that a certain degree of interaction exists, although it does not seem to be a result of chemical interaction. The designed fibers could be potentially used for the development of scaffolds for tissue engineering applications.