Objectives: It is our aim to understand the mechanisms that make calcium phosphates, such as bioactive calcium hydroxyapatite (HA), and biphasic calcium (BCP) and p-tricalcium (I3-TCP) phosphates, desirable for a variety of biological applications, such as the filling of bone defects. Methods: Here, we have characterized these materials by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR), time-of-flight secondary ion mass spectroscopy (TOP-SIMS) and laser granulometry. Results: SEM shows clearly that BCP is a matrix made of macro-organized microstructure, giving insight to the specially chosen composition of the BCP that offers both an adequate scaffold and good porosity for further bone growth. As revealed by laser granulometry, the particles exhibit a homogeneous size distribution, centered at a value somewhat larger than the expected 500 p.m. XPS has revealed the presence of adventitious carbon at all sample surfaces, and has shown that Ca/P and 0/Ca ratios in the outer layers of all the samples differ significantly from those expected. A peak-by-peak XPS comparison for all samples has revealed that TCP and BCP are distinct from one another in the relative intensities of their oxygen peaks. The PO/PO i and CaOH+/Ca+ TOF-SIMS intensity ratios were used to distinguish among the samples, and to demonstrate that the OH- fragment, present in all the samples, is not formed during fragmentation but exists at the sample surface, probably as a contaminant. Conclusions: This study provides substantial insight into the nanoscale surface properties of BCP, HA and 13-TCP. Further research is required to help identify the effect of surfaces of these bioceramics with proteins and several biological fluids. Clinical relevance: The biological performance of implanted synthetic graft bone biomaterials is strongly influenced by their nanosurface characteristics, the structures and properties of the outer layer of the biomaterial. (C) 2013 Elsevier Inc. All rights reserved.