Two structured manganese oxides (Birnessite and Todorokite) containing Co have been studied in the steam reforming of ethanol. It has been found that both materials are active in the hydrogen production, exhibiting high values of conversion of ethanol and selectivities to hydrogen (100% and 70%, respectively). The best results have been obtained with the catalyst based on Todorokite material. Characterization by DRX, BET area, TPR and TEM has allowed to find that the excellent performance exhibited by this material could be attributed to the lower size of the Co metallic particles present in this sample (6 nm vs 12 nm in Birnessite). This lower size could be related to the especial microporous structure of Todorokite precursor, which could provide high-quality positions for the stabilization of the Co metal particles during calcination and reduction steps. Catalytic deactivation has also been considered. Deactivation was found higher for Todorokite-based catalyst, which presented the largest amount of deposited carbon (26.2 wt% for Co-TOD vs 10.6 wt% for Co-BIR). On the other hand, the degree of metal sintering was found similar in both catalysts. Therefore, the deactivation of the catalysts has been attributed primarily to the deposition of coke. The results presented here show that it is possible to prepare new catalysts based on manganese oxides with Birnessite and Todorokite structure and promoted with Co with high catalytic performance in the steam reforming of ethanol. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.