Preparation and characterization of a controlled release system of rhodium (II) citrate, acetate. propionate, butyrate and their inclusion or association compounds with cyclodextrin (CD) are described. The porous hydroxyapatite (HA) was characterized by X-ray powder pattern diffraction, FTIR and solid state 31P NMR. Scanning electron microscopy and gas adsorption analysis (BET) were also performed. Release profiles of rhodium (II) carboxylates and their inclusion or association compounds from HA matrix were obtained at different drug loadings (5% and 10%). These were reasonably consistent with a diffusion model. This analysis, mainly using rhodium (II) citrate and butyrate, showed that the strategy of using CDs with a HA matrix may offer a useful new method for the controlled release of these compounds, and hence an alternative strategy for the controlled release of chemotherapeutic agents containing toxic metals. This may be a valuable new technique for localized anti-tumour chemotherapy that minimizes the side effects of such agents.