Copper, iron and cobalt supported on activated carbon materials are compared as catalysts in methanol decomposition in view of their potential application as intelligent carriers of hydrogen. The activated carbon supports were obtained from renewable agriculture waste (peach shell) or coal treatment by-products (coal tar pitch). The parent activated carbons and their transition metal modifications were characterized by nitrogen physisorption, XRD, UV–Vis, FTIR, Mössbauer spectroscopy and TPR in hydrogen, and the surface functional groups were determined by the Böhm method. It was assumed that the formation of transition metal modified activated carbon catalysts is a complex process which proceeds during the preparation procedure with the activity of the support and also during the catalysis by the influence of the reaction medium. The decisive effect of carbon basal planes over the texture and surface functionality of the support on the formation of transition metals active phase was assumed. Among the studied materials, cobalt modifications exhibited excellent catalytic activity and selectivity in methanol decomposition to H2 and CO despite the nature of the activated carbons used.