Reactions of the trityl cations with germanes afford the germylium ions [R₃Ge][B(C₆F₅)₄] (1a: R = Et, 1b: R = Ph, 1c: R = nBu). These compounds react with germane or fluorogermane to give polynuclear species, which are sources of the mononuclear ions, The latter convert with phosphines to yield the [R₃Ge-PR₃]⁺ (4a: R = Et, 4b: R = Ph) cations. Catalytic dehydrofluorination reactions were observed for the C–F bond activation of fluoroalkanes when using germanes as hydrogen source.