Electrochemical ozone production (EOP) is a promising technology for the removal of contaminants in wastewater. However, traditional two-dimensional anodes for EOP are restricted by their reliance on substrates and limited surface area, thus exhibiting poor stability and efficiency. Herein, a novel three-dimensional Sb–SnO2 with Cu and Ni co-doped (3D CuNi-ATO) was synthesized via a facile pressing-sintering method without the Ti substrate. 3D CuNi-ATO had a specific surface area two orders of magnitude higher than conventional CuNi-ATO/Ti, as well as the significant capability of EOP that differs from intrinsic 3D ATO. This endowed 3D CuNi-ATO with the capability to remove tetracycline with a pseudo-first-order rate constant of 0.033 min−1 under a low current density of 5 mA cm−2 within 120 min, which was far more efficient than that by 3D ATO and other two-dimensional anodes reported. The 3D CuNi-ATO was confirmed stable in 100 cycles and had an accelerated service lifetime of over 1100 h versus 83 h of CuNi-ATO/Ti. The degradation of tetracycline in complex matrix and flow-through reactors further revealed the promising potential of 3D CuNi-ATO to be applied in scenarios of practical application and continuous high-rate treatment.