The purpose of this study was to develop bioceramics with a well-defined porous structure in order to control drug loading and release over time. Porous structures were obtained through colloidal processing, using polymethyl methacrylate (PMMA) microspheres as templates (core) and hydroxyapatite (HA) nanoparticles as inorganic building blocks (shell). Dispersed HA suspensions were prepared and their electrokinetic properties were studied to determine a dispersant giving a high positive zeta potential (opposite to the negative zeta potential of PMMA). Upon mixture of well-dispersed HA and PMMA suspensions of opposite charge, core-shell structures were formed via heterocoagulation. After consolidation, polymers were removed by calcination, resulting in a porous structure of controlled size and distribution.