Finding effective and practical ways to remove contaminants in the water is a challenging problem, therefore, the construction of recyclable materials has been paid attention to in the practical application of advanced oxidation processes. A three-dimensional hollow tubular surface-loaded cobalt/cotton carbon fiber composite (Co-CCF-600) is successfully prepared by carbonization, which can effectively activate PMS to degrade CBZ. The synthetic Co-CCF-600 degrades 93.47% of CBZ within 60 min. It is worth noting that Co-CCF-600 has good stability and high catalytic activity after 5 cycles, which is attributed to the synergy between Co species (Co0 and CoO) and CCF. In addition, both radical and non-radical processes contribute to the degradation of CBZ, and SO4•− plays a dominant role. After a 118 h wastewater degradation experiment, the Co-CCF-600/PMS system still maintains high degradation efficiency and stability. Overall, this study provides an environmentally friendly, low-cost cobalt/carbon fiber material for the removal of CBZ in wastewater and provides a practical solution for environmental remediation.