The influence of synergistic effect between dodecylamine (DDA) and sodium oleate (NaOl) on the hydrophobicity of fluorapatite (FA) was investigated with contact angle, surface tension, XPS and zeta potential studies. The role of pH and the mixing ratio of surfactants on the synergistic behavior were considered. Basing on the contact angle results the suitable pH for the NaOl-DDA mixture was pH 9.5. A further study indicated that the 3:7 DDA-NaOl mixtures could notably improve the contact angle comparing to that only with DDA or NaOl. In the solution of this mixture, the DDA cation and DDA molecule both adsorb at the FA surface as revealed by the XPS spectra results. The zeta potential analysis further suggested that the adsorption of oleate at the FA surface was also improved. The presence of DDA cation and DDA molecule was expected to result in a uniform packing of surfactants at the FA surface.