Scaffolds suitable for tissue engineering applications like dermal reconstruction were prepared by Thermally Induced Phase Separation (TIPS) starting from a ternary solution PLLA/dioxane/water. The experimental protocol consisted of three consecutive steps, a first quench from the homogeneous solution to an appropriate demixing temperature (within the metastable region), a holding stage for a given residence time, and a final quench from the demixing temperature to a low temperature (within the unstable region). A large variety of morphologies, in terms of average pore size and interconnection, were obtained upon modifying the demixing time and temperature, owing to the interplay of nucleation and growth processes during the residence in the metastable state. An interesting combination of micro and macroporosity was observed for long residence times in the metastable state (above 30 min at 35 degrees C). Preliminary degradation tests in a biological mimicking fluid (D-MEM with bovine serum) showed a significant weight loss during the initial stages (ca. 30% in 30 days) related to the degradation of the amorphous part, followed by a negligible weight loss in the next days (few percent from 30 to 60 days).