The present study shows that the positrophilic electrons of a molecule dock with the positron attractive potential region in the annihilation process at the plane-wave approximation level of theory. The positron-electron annihilation processes of both polar and non-polar fluorinated methanes (CH4-nFn, n = 0, 1, ..., 4) are studied. The predicted gamma-ray spectra of these fluorinated methanes agree well with experiment, which provides further evidence that the positrophilic electrons of a molecule dock at the negative end of a bond dipole, independent of the molecular dipole moment in the annihilation process.