In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) — titanium dioxide (TiO2). Under the UV light irradiation, the photoinduced electrons generated from TiO2 could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO4•−), hydroxyl radical (•OH) and singlet oxygen (1O2) in the UV/PMS/20%CNT-TiO2 system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO2 system (0.18 min−1) was 23.7 times higher than that of the PMS/Co3O4 system (0.0076 min−1). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO2 system.