Macroporous alumina materials were fabricated via colloidal processing using polymer spheres as the template and ceramic particles as the building blocks. The influence of the suspension conditions and volume ratio of the polymer/ceramic particles on the formation of the pore structure has been investigated. The results showed that the suspension conditions have a significant effect on the pore morphology. A well-defined three-dimensional, ordered porous structure with a controllable pore size and porosity could be obtained through the hetero-coagulation, self-assembled processing of the polymer/ceramic particles. The pore size and porosity could be easily tailored by varying the polymer size and the volume ratio of the polymer/ceramic particles.