The gas-phase oxidative dehydrogenation of ethylbenzene to styrene was carried out by using as catalyst a series of metal phosphates (Al, Fe, Ni, Ca and Mn) and stoichiometric (Al/Fe = Al/Ca = 1) mixed systems: FeAl(PO4)(2) and Ca3Al3(PO4)(5), that were prepared by an ammonia gelation method. Their amorphous character was determined through several physical methods: nitrogen adsorption, DRIFT and XRD patterns. These results were compared to those obtained with 24 commercial inorganic solids (several metal oxides, sulfates and phosphates). Reactions were also carried out without oxygen, under non-oxidative conditions, where the catalytic activity was always appreciably lower than under oxidative conditions. Experimental results indicated that the oxidative gas-phase dehydrogenation of ethylbenzene, to styrene could be related to the total number of acid and basic sites of catalysts, so that this reaction probably needs selected acid-basic pairs for coke formation, where the oxidative dehydrogenation process is developed. The main practical conclusion of the catalyst screening was that the best results were obtained with the synthesized amorphous AlPO4, where 43% ethylbenzene conversion and 99.7% styrene selectivity were achieved. A very reduced number of commercial inorganic solids like Al-2(SO4)(3), Cr-2(SO4)(3), Fe-2(SO4)(3), NiSO4, Al2O3 and Fe2O3 Were also able to obtain an acceptable catalytic behavior, with conversions ranging between 18 and 23% and selectivity in the 95-100% range. Among the other synthesized solids, Ni-3(PO4)(2)-A-450 was the only metal phosphate exhibiting results in such a ran-e. All the other catalysts studied were rather inactive and/or selective. Additional experiments carried out at longer times on stream (3.5 h) and longer contact times (W/F 0.254 and 0.654) confirmed the superior catalytic behavior of amorphous AlPO4, Consequently, this solid could be a good candidate for application as a catalyst in the industrial oxydehydrogenation of ethylbenzene to styrene. (c) 2006 Elsevier B.V. All rights reserved.