A Cu2O superstructure is constructed through a recrystallization-induced self-assembly strategy. Single Cu2O superstructure particle exhibits an outstanding surface-enhanced Raman spectroscopy performance with the limit of detection as low as 10−9 mol L−1 and metal comparable enhancement factor (8 × 105) due to the synergetic effect of vacancies defect-facilitated charge-transfer process and copper vacancies defect-induced electrostatic adsorption.