Heterostructure composite catalysts have shown great potential in activating peroxymonosulfate (PMS) to effectively remediate organic contaminants. However, the construction of high-performance composites with a heterostructure interface using simple and rapid strategies remains a challenge. This study introduces a straightforward and environmental-friendly approach to prepare NiCo/CoNiO2 heterojunction integrated carbon nanotubes (NiCo/CoNiO2@CNTs) through a solid-phase microwave carbon bath process, where CNTs serve as a substrate and microwave adsorption material. The NiCo/CoNiO2@CNTs/PMS system demonstrates exceptional performance, achieving a removal rate of 95.9 % within 30 min in degrading tetracycline (TC) with PMS activation. Synergistic effects between the CoNi alloy and CoNiO2 promote the Co3+/Co2+ and Ni3+/Ni2+ redox cycles, boosting the catalyst’s activity and reusability. Moreover, the NiCo/CoNiO2@CNTs/PMS system demonstrates high resistance to various solution pH levels, inorganic anions and humic acid. The catalytic oxidation of TC involves radical and non-radical pathways, with the latter dominating the degradation process. Three possible pathways generate thirteen intermediate products during TC destruction. Toxicity assessment reveals a significant reduction in the toxicity of TC-contaminated water after degradation over the system. The current study not only presents an effective strategy for fabricating heterojunction composite materials but also offers an efficient oxidation system for remediating antibiotic pollutants.