The catalytic activity in the conversion of biomass devolatilization products to syngas of a novel alumina supported Rh–LaCoO3 catalyst has been investigated in a double fixed bed reactor system. A catalytic screening has been carried out in order to define the limits of both operation parameters and Rh load to obtain a complete tar conversion associated with the lowest coke deposition taking into account either efficiency or costs of the material. The effect of rhodium load has been investigated in the range 0.1–1 wt.%. The study of the operation parameters has been performed by modifying the reaction temperature (500–700 °C), the catalyst amount (0.25–1 g) and the N2 flow rate (12–60 Nl h-1). The catalyst still provides good performances in tar and light hydrocarbons conversion when the temperature is lowered down to 600 °C. At 700 °C a complete tar conversion can be obtained both reducing the 1% Rh–LaCoO3 catalyst amount in the reactor to 0.5 g and decreasing the Rh load down to 0.1 wt.%. TPR and DRIFT analyses have been performed to characterize the nature of Rh and to correlate this feature to the catalytic performances.