Calcium phosphate (CaP) based hybrid materials have been synthesized through a precipitation method in aqueous medium in the presence of the anionic surfactant sodium dodecylbenzene sulfonate (SDBS) as structure directing agent. Parameters of synthesis, such as Ca/P molar ratio, surfactant concentration and initial pH, have been investigated trying to get mesostructured CaP phases. A lamellar‐like hybrid mesophase consisting in several wavy layers of apatite or apatite‐brushite nanoplates was successfully obtained. Materials have been characterized by several physico‐chemical techniques. A potential application of these lamellar calcium phosphate based hybrids can be as matrixes in drug delivery systems with the possibility of loading hydrophobic drugs in the organic interlayers. To evaluate their potential as biomaterials, the biocompatibility of two hybrids has been studied in vitro with human Saos‐2 osteoblasts. Cell assays showed that, upon the appropriate synthesis and stabilization conditions, a biocompatible CaP and SDBS mesolamellar hybrid can be prepared. Mesostructured lamellar calcium phosphates have been prepared via surfactant templating with sodium dodecylbenzenesulfonate. Synthesis parameters were optimized leading to a novel hybrid material consisting of mesolamellar apatite. The hybrids biocompatibility has been evaluated in vitro with human osteoblasts showing that biocompatible hybrids can be prepared, therefore suggesting their possible application as matrixes in drug delivery systems.