This work focuses on investigation of calcium phosphate compounds with different Ca/P ratios (1.39-1.77). Additionally, hydroxyapatite impregnated with tungsten oxide was also investigated. The structural, textural, and surface properties of these materials have been fully characterized using appropriate techniques (low-temperature adsorption-desorption of nitrogen, X-ray diffraction analysis (XRD). X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and temperature-programmed reduction (TPR)). Adsorption microcalorimetry of NH3 or SO2 was used to estimate the population, strength and strength distribution of acid and basic sites. The nature of acidic sites was determined through the adsorption/desorption of pyridine, followed by infrared spectroscopy. Catalytic performance of the catalysts was tested in the gas phase dehydration of glycerol with the intention of finding correlations between catalytic activity and surface acid-base features. Results show that Ca/P ratio, beside the already known influence on acidic/basic features, also influences red-ox properties of these materials. The investigation performed here proved that, in order to get acrolein - with high selectivity - which is formed on acid sites, it is not only necessary to provide acidity, but also to hinder basic sites. Our results also show that reducing of number and strength of acid centers increases the yield of other desired product, acetol. (C) 2012 Elsevier B.V. All rights reserved.