Novel hybrid aerogels consisting of the bioderived polymers chitosan, pectic acid or alginic acid and silica have been synthesized as clear monoliths from clear gels by supercritical fluid extraction. These renewable resource polymers, which are soluble and typically unassociated in aqueous systems, are separately arranged in aerogel scaffolding. This makes them exposed and available for reactions that in some cases would not be possible in aqueous systems. Thus, it is possible to react the amine groups of chitosan, a polymer derived from chitin, with isocyanate-terminated prepolymers to form urea linkages and to form new linked chitosan materials. Following the reactions, the scaffold can be dissolved and the new material isolated. Variations lead to hydrophobic or hydrophilic materials. The reactions of aerogel scaffolded bioderived polymers to form urethane-or amide-group linked materials also will be presented and the properties of newly formed materials will be described. Further reactions enabled by the approach, including ones leading to radiation curable polymeric systems will be presented.