The formation of ethers in radiolysis of methane, ethane, and propane in the presence of either methanol or ethanol was studied in the gas-phase using a conventional approach based on analysis of the stable products. A mechanism is established to be ionic and probably involves condensations of ions originating from alkanes with alcohols, solvation of ionic complexes by alocohols, and finally supersession of ethers by alcohols in equilibrium exchanges. For want of mass spectrometric data the identity of ionic precursors remains speculative, although there is strong evidence that C2H5+ions are not involved. In propane another ionic mechanism contributes to the formation of C2H5O-n-C3H7; in this case the ionic precursor originates from the alcohol rather than from the alkane.