The Fischer-Tropsch synthesis (FTS) for the production of widely distributed hydrocarbons through the catalytic hydrogenation of carbon monoxide (CO) has been intensively and extensively explored. This is attributable to its immense theoretical as well as practical importance. Naturally, such exploration would be greatly facilitated if the feasible or dominant catalytic pathways (mechanisms) of FTS can be determined. The stoichiometrically feasible and independent catalytic pathways (IPi's) of FTS have been exhaustively identified via the rigorous graph-theoretic method based on P-graphs (process graphs). The most extensive set of elementary reactions available, which numbers 26, has yielded 24-IPi's in less than 1 s on a PC. The plausibly dominant pathways have been selected from the stoichiometrically feasible pathways through the analysis of their activation energies. Naturally, the dominant pathway or pathways need ultimately be discriminated among these plausibly dominant pathways via various means, e.g., in situ spectroscopic measurements of intermediates. (C) 2009 Elsevier Ltd. All rights reserved.