Tailoring the microstructure of porous materials is essential in order to fulfill the various requirements in industry and daily life. Here we present the macroporous self-setting aluminum trihydroxide (ATH) foams which were fabricated by a direct foaming technique. Sodium dodecyl sulfate (SDS) was used as a surfactant and ATH particles were partially hydrophobized by the adsorption of SDS on its surface. Upon frothing, the foam was stabilized by ATH particles. SDS is a long chain surfactant and has low adsorption energy; therefore the microstructure of the foam was set immediately by the addition of ordinary Portland cement. The self-setting ATH foam obtained by this technique has an average cell size ranging from 69 to 140 µm and porosity in the range of 86 to 93%.