In combination with copper(II) ions, disulfiram (DSF) has been reported to be a potentially potent anticancer agent based on in vitro results. The interaction of DSF with copper(II) chloride in solution has been studied using a range of spectroscopic techniques. There is strong evidence for the rapid formation of the bis(N,N-diethyl dithiocarbamato)copper(II) complex in situ. Kinetic experiments were used to determine rate laws for the reaction that give insight into the mechanism of the process which may help to explain the observed in vitro cytotoxicity.