Novel syntactic foams for potential building material applications were developed using starch as binder and ceramic hollow micro-spheres available as waste from coal-fire power stations. Foams of four different micro-sphere size groups were manufactured with either pre-or post-mould gelatinization process. They were of ternary system including voids with a foam density range of approximately 0.33-0.44 g/cc. Compressive failure behaviour and mechanical properties of the manufactured foams were evaluated. Not much difference in failure behaviour or in mechanical properties between the two different processes (pre- and post-mould gels) was found for a given binder content. Compressive failure of all syntactic foams was of shear on plane inclined 45 degrees to compressive loading direction. Failure surfaces of most syntactic foams were characterized by debonded micro-spheres. Compressive strength and modulus of syntactic foams were found to be dependant mainly on binder content but mostly independent of micro-sphere size. Some conditions of relativity arising from properties of constituents leading to the rule of mixtures relationships for compressive strength and to understanding of compressive/transitional failure behaviour were developed. The developed relationships based on the rule of mixtures were partially verified. Some formation of starch webs on failure surfaces was discussed.