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Activated carbons with different textural and chemical surface characteristics were synthesized from waste biomass and low rank coals, and furthermore used as a host matrix for cobalt species, varying the preparation and modification methods. The obtained activated carbons and modified samples were characterized by complex of various physicochemical methods, such as: low temperature physisorption of nitrogen, XRD, EPR, XPS, UV-Vis and TPR with hydrogen. Boehm method was applied for qualitative and quantitative determination of oxygen-containing groups on the carbon surface before and after cobalt deposition. The catalytic properties of cobalt modifications were tested in methanol decomposition. The dominant effect of activated carbon texture over the surface chemistry on the state and catalytic behaviour of cobalt species was discussed.