The catalytic performances of Co/MgO catalysts for the steam reforming of naphthalene were investigated. The results of characterizations (TPR, XRD, CO adsorption, and CO-TPD) showed that large-sized Co metal particles were formed over the catalysts pre-calcined at 873 K with high Co loading via reduction Of Co-3-O-4 and MgCo2O4 phases. A few Co metal particles were obtained over the catalysts pre-calcined at 1173 K with all Co loading values after reduction. The catalytic performances data showed that 12 wt.% Co/MgO catalyst pre-calcined at 873 K exhibited the best catalytic performance (conv., 23%, 3 h) for the steam reforming of naphthalene among the catalysts tested in this study, due to the existence of Co metal and the low amounts of coke deposition. On the other hand, the data also revealed that the reaction of steam reforming of naphthalene proceeds over all Co-loaded catalyst pre-calcined at 1173 K initially; however, the deposition of the polymer of Q,H radicals and the oxidation of catalysts by H2O led to the decrease of activity. It should be noted that 12 wt.% Co/MgO catalyst pre-calcined at 873 K showed high and stable activity under the low steam/carbon mole ratio (0.6), with H-2 and CO2 as main products. These two excellent advantages serve to increase the overall biomass gasification system energy efficiency and allow using the product gas for fuel cell system. Thus, Co catalyst is a promising system for the steam reforming of naphthalene derived from biomass gasification as a second fixed catalytic bed. (C) 2004 Elsevier B.V. All rights reserved.