The interaction of AlF4 superhalogen with methane and its chloro derivatives is investigated theoretically. Strong interaction and formation of ionic compounds are expected for all chloro substituted methane molecules, whereas the interaction of AlF4 with CH4 results in creation of a weakly bound complex. The generated systems (excluding that with CCl4) correspond to the intermediate products and should further evolve (via the inter-fragment proton transfer) to considerably more stable radical products. The performed analysis indicates a key-role of the AlF4 as the trigger-compound capable of initiating the radical-substitution chain of reactions in methane, its chloro derivatives, and likely other hydrocarbons. (C) 2014 Elsevier B.V. All rights reserved.