Methanol- and temperature-induced dissolution–recrystallization structural transformation (DRST) was observed among two novel CuII complexes. This is first time that the combination of X-ray crystallography, mass spectrometry and density functional theory (DFT) theoretical calculations has been used to describe the fragmentation and recombination of a mononuclear CuII complex at 60 °C in methanol to obtain a binuclear copper(II) complex. Combining time-dependent high-resolution electrospray mass spectrometry, we propose a possible mechanism for the conversion of bis(8-methoxyquinoline-κ2
N,O)bis(thiocyanato-κN)copper(II), [Cu(NCS)2(C10H9NO)2], Cu1, to di-μ-methanolato-κ4
O:O-bis[(8-methoxyquinoline-κ2
N,O)(thiocyanato-κN)copper(II)], [Cu2(CH3O)2(NCS)2(C10H9NO)2], Cu2, viz. [Cu(SCN)2(L)2] (Cu1) → [Cu(L)2] → [Cu(L)]/L → [Cu2(CH3O)2(NCS)2(L)2] (Cu2). We screened the antitumour activities of L (8-methoxyquinoline), Cu1 and Cu2 and found that the antiproliferative effect of Cu2 on some tumour cells was much greater than that of L and Cu1.