This study investigated the in vitro degradation of both solid PPF networks and porous PPF scaffolds formed by photoinitiated cross-linking of PPF polymer chains. Three formulations of scaffolds of differing porosity and pore size were constructed by varying porogen size and content. The effects of pore size and pore volume on scaffold mass, geometry, porosity, mechanical properties, and water absorption were then examined. Throughout the study, the solid networks and porous scaffolds exhibited continual mass loss and slight change in length. Porogen content appeared to have the greatest effect upon physical degradation. For example, scaffolds initially fabricated with 80 wt % porogen content lost approximately 30% of their initial PPF content after 32 weeks of degradation, whereas scaffolds fabricated with 70 wt % porogen content lost approximately 18% after 32 weeks of degradation. For all scaffold formulations, water absorption capacity, porosity, and compressive modulus were maintained at constant values following porogen leaching. These results indicate the potential of photo-cross-linked PPF scaffolds in tissue engineering applications which require maintenance of scaffold structure, strength, and porosity during the initial stages of degradation.