The Ca* + CH3F --> CaF* + CH3 reaction was studied both experimentally and theoretically. The reaction was photoinduced in Ca...CH3F complexes, which were illuminated by a tunable laser in the range 18 000-24 000 cm-1. The absorption band that leads to the reaction extends between 19 000 and 23 000 cm-1. It is formed of three broad overlapping structures corresponding to the excitation of different electronic states of the complex. The two structures of lowest energy were considered in detail. They are associated with two series of respectively 2 and 3 molecular states correlating to Ca(4s3d 1D) + CH3F at infinite separation between Ca and CH3F. The assignment of these structures to specific electronic transitions of the complex stemmed from theoretical calculations where the Ca...CH3F complex is described by a linear Ca-F-C backbone. 2D potential energy surfaces were calculated by associating a pseudopotential description of the [Ca2+] and [F7+] cores, a core polarization operator on calcium, an extensive Gaussian basis, and a treatment of the electronic problem at the CI-MRCI level. All the excited levels correlating to the 4s2 1S, 4s3d 1D, and 4s4p 1P levels of Ca in the Ca + CH3F channel were documented in a calculation that explored the rearrangement channels where either Ca + CH3F or CaF + CH3 are formed. Then, wavepacket calculations on the 2D-PES's allowed one to simulate the absorption spectrum of the complex, in an approximation where the various electronic states of the complex are not coupled together. The assignment above stemmed from this. The second outcome of the calculation was that whatever the excited level of the complex that is considered, the reaction has to proceed through energy barriers. The electronic excitation of the complex on the red side of the absorption band does not seem to deposit enough energy in the system to overcome these barriers (even the lowest one) or to stimulate tunneling reactions. An alternative reaction mechanism involving a transfer to triplet PES's is proposed.