Catalytic steam reforming of bioethanol seems to be a promise option to produce renewable hydrogen; however efficient catalysts are still under development. Recently, manganese oxide based materials (MO) are the subject of intense research as low cost, efficient, and environmentally friendly catalysts. Among them MO with layer and tunnel structure have received significant attention due to their excellent catalytic activity. Specifically, we have explored the catalytic performance of two MO containing Ni (Birnessite and Todorokite). We find that both materials are highly active and selective to produce hydrogen by steam reforming of bioethanol. Their characterization by DRX, BET area, TPR, and TEM, has allowed to find that the excellent performance exhibited by these materials could be attributed to the especial structure of these MO, which would provide high-quality positions for the stabilization of the Ni metal particles.