A β-zeolite/polystyrene composite material was synthesized by co-deposition of mono-disperse polystyrene spheres and nano β-zeolite particles in aqueous suspension on a vertical substrate. Macro-porous β-zeolite was obtained after the polystyrene template was removed by calcination. The micro/macro-pore structure of the prepared β-zeolite was highly ordered. In comparison with other assembly methods, the co-deposition method could obtain a highly ordered macro-porous material with relatively large zeolite filling particles, and therefore the co-deposition of particles with different size is a promising method for the fabrication of macro-porous materials.