The preparation and characterization of porous scaffolds from chitosan-PCL blends by freeze extraction, freeze gelation and freeze drying is reported. Using freeze extraction, stable structures were obtained only from PCL, but these were not porous. No stable scaffolds were obtained using the freeze gelation process. Stable scaffolds of chitosan/PCL mixtures could not be obtained using 77% acetic acid by any of these techniques. With 25% aqueous acetic acid, stable scaffolds of chitosan/PCL mixtures were obtained by the freeze drying technique. The stability and pore morphology of freeze dried scaffolds were dependent on the relative mass ratio of chitosan and PCL. A chorioallantoic membrane assay showed that formed 3D chitosan/PCL mixtures were not toxic to vasculature.