The mass spectra of 13 heterofulvalenes are reported. The spectra show great similarities within the selenium and within the sulphur series. The main difference between the selenium and the sulphur compounds results from the more facile loss of selenium compared with sulphur, and from the first fragmentation of the molecular ion, as the selenium fulvalenes lose an alkyne molecule, whereas the sulphur fulvalenes first lose an (SĊR) radical. An important feature of the spectra of the simple heterofulvalenes is the formation of a rearrangement ion by migration of a heteroatom. The mechanism was elucidated by 13C labelling and is discussed in detail.