The magnesium-cobalt phosphates Co,Mg3-x(PO4)(2) belonging to the olivine-type structure were synthesized by coprecipitation and then investigated in the oxidative dehydrogenation (ODH) of ethane and propane. The best yields, with the exception of Co0.5Mg2.5(PO4)(2). were achieved with the compositions ranging between 1 less than or equal to x less than or equal to 2.5. Magnesium phosphate Mg-3(PO4)(2) displayed no activity and pure cobalt phosphate Co-3(PO4)(2) was found to be the less active component of the solid solution. Comparison of the catalysts performances showed that they all have similar activity in ethane and propane ODH. albeit, they are more selective in propylene than in ethylene production. The CoxMg3-x(PO4)(2) solid solution was also studied, for characterization purposes, in butan-2-ol conversion. The samples presented acid-base properties due essentially to the (PO-H) groups but they do not bear conventional redox centers. All the catalysts were active at low temperatures in the alcohol dehydration. The dehydrogenation activity versus the phosphates composition displayed two maxima around x = 1 and 2, respectively. Similar striking behavior was also observed in ethane and propane ODH. UV-visible investigations of CoxMg3-x(PO4)(2) showed, in agreement with the XRD data, that the Co2+ ions are distributed in the phosphate framework between six- and five-coordinated sites. The cobalt atoms in the five-coordinated sites Co(5) and their Co(5)-Co(5) interatomic distances were assumed to play the main role in the C-H bond activation and the appearance of maxima in the activity. Magnesium cations presumably intervene in acid-base properties of the samples and O-2 activation. Characterization of the samples showed that they do not undergo any noticeable transformation after the catalytic tests.