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Abstract Using time-of-flight multiple electron and ion coincidence techniques in combination with a helium gas discharge lamp and synchrotron radiation, the double ionisation spectrum of disulfur (S $$_2$$ 2 ) and the subsequent fragmentation dynamics of its dication are investigated. The S $$_2$$ 2 sample was produced by heating mercury sulfide (HgS), whose vapour at a suitably chosen temperature consists primarily of two constituents: S $$_2$$ 2 and atomic Hg. A multi-particle-coincidence technique is thus particularly useful for retrieving spectra of S $$_2$$ 2 from ionisation of the mixed vapour. The results obtained are compared with detailed calculations of the electronic structure and potential energy curves of S $$_2^{2+}$$ 2 2 + which are also presented. These computations are carried out using configuration interaction methodology. The experimental results are interpreted with and strongly supported by the computational results.