Different apatitic calcium phosphates used as direct compression excipients have been developed in the last years. The difficulty to obtain reproducible synthesis explains their approximative and irregular composition. TRI-TAB(R) commercial grade called anhydrous tricalcium phosphate is associated to a chemical formula corresponding to a mixture of tricalcium phosphate (Ca-3(PO4)(2)) and calcium hydroxide (Ca(OH)(2)). The chemical analysis shows that it is hydroxyapatite (Ca-10(PO4)(6)(OH)(2)). The purpose of this work is to rationalize the chemical and physical natures of apatitic calcium phosphates used in direct compression, and thus their technological properties. Apatitic calcium phosphates differing in their Ca/P molar ratio (from 1.500 i.e. tricalcium phosphate to 1.667 i.e. hydroxyapatite) have been synthesized and their compression properties have been analysed. The results have been compared to those of TRI-TAB V. They pointed out the importance of the chemical nature contribution. Tricalcium phosphate-based materials exhibited an excellent compactibility when not calcined. Uncalcined hydroxyapatite had similar properties than TRI-TAB(R), that is intermediate. Calcined tricalcium phosphate and hydroxyapatite showed a low compaction ability. It appears that the perfect chemical and physical control of the material is important in particle design to rationalize and optimise the tablet formulation as well as the process.