The mass spectral fragmentation of five dinuclear Cu(II) complexes of the general formula [Cu₂(Rdtc)tpmc] (ClO₄)₃, where tpmc and Rdtc refer to N, N, N, N-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and piperidine- (Pipdtc), 4-morpholine- (Morphdtc), 4-thiomorpholine- (Timdtc), piperazine- (Pzdtc), or N-methylpiperazine- (N-Mepzdtc) dithiocarbamates, respectively, has been investigated. The results were shown to be of mechanistic significance, clarifying the major products of their fragmentation. A possible mechanism entails a multi-step decomposition process that can be separated into individual steps depending on their molecular structures. Every step is determined to some extent by the nature of the intermediates.