The gas-phase methylation of 2-and 3-methyl-pyrroles (2P and 3P),-furans (2F and 3F), and- thiophenes (2T and 3T) by (CH3) 2F+ ions, from γ radiolysis of CH3F, has been investigated at pressures ranging from 50 to 760 Torr, in the presence of a thermal radical scavenger (O2) and variable concentrations of an added base (NMe3: 0-10 Torr). The mechanism of the methylation process is discussed and the intrinsic positional selectivity of the (CH3) ...