The need for tissue engineering scaffolds cannot be underestimated. Current approaches usually involve choosing a material and optimizing production techniques to produce appropriate pore structures. This has its advantages, but hinders rapid adaptation to the needs of diverse tissue engineering applications or preparation of model systems where structure and composition may be independently varied to establish much-needed structure-composition-properties relations. We apply organic sol-gel chemistry to address these issues, and demonstrate the ability to prepare robust, highly porous polymer xerogels with a range of pore structures, compositions, and properties, with independent variations possible. We present the results of structural analyses (mercury intrusion porosimetry and scanning electron microscopy) as well as cell culture studies, the latter indicating significant cytocompatibility in some systems and confirming the utility of the approach. Shown is an image of an NIH 3T3 fibroblast that has colonized one of our polyester-ester thermoset xerogels.