Bio-based biodegradable resin was prepared by condensation of gelatinized starch and furfuryl alcohol, in presence of glyoxal as crosslinker. The resin was blown with different foaming agents and/or flame retardants such as phosphoric or boric acids, to produce environmentally friendly foam structures, given the bio-based nature of the main components, which are both derived from corn. Scanning electron microscopy (SEM) imaging of the samples revealed closed cell structure with a smooth surface. The excellent pulverization ratio and appreciable compression strength compared with the phenol-formaldehyde (PF)-based foam, render them strong candidates for building materials. Different investigations proved characteristics such as low thermal conductivity, good stability against thermal degradation and high limiting oxygen index (LOI) values, support the liability of such structures for application as heat insulating and fire-resistive materials.