Electrospray ionisation (ESI) mass spectra obtained for solutions containing curcumin, copper cation and other metal cations, namely Co2+, Ni2+, Mn2+ and Zn2+, have shown an abundant curcumin molecular ion at m/z 368. This ion was not formed for solutions containing curcumin and copper cations or for those containing curcumin and other metal cations. To the best of our knowledge, it is the first example of a system in which copper cations and other metal cations promote formation of organic radical cation under ESI conditions.