CdIn2S4 (CIS) has attracted much attention in the photocatalysis research field due to its structural stability and photoelectric properties. However, it's difficult to recycle when after usage, so application of CIS photocatalysis in removing volatile organic compounds (VOCs) is still limited and the literature on applying carbon nanofibers (CNFs) as electron acceptor is scarce. In this study, a novel CIS/CNFs composite was synthesized via a simple hydrothermal method. X-ray diffraction (XRD), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) were applied to characterize the structure, microtopography and composition of CIS/CNFs photocatalyst prepared. The results showed that CNFs with the size of about 300 nm were favorable connected with CIS to form 3D conductive network and CIS particles with the average size of 100 nm grew onto the surface of CNFs uniformly. Results of photocatalytic degradation tests indicate that under visible light irradiation, degradation of toluene reached the optimal level of 86% as the CIS doped with 3% CNFs. It proved that the composite material prepared had an excellent photocatalytic recycle efficiency via repeated experiments. Furthermore, 95% removal efficiency was achieved as 200 ppm ozone was added into the system and mineralization rate are also improved. Derived from the intermediates detected, possible pathways of toluene degradation were proposed. Hence, this study presents a new method to synthesize photocatalyst with visible-light driven ozone-enhanced photocatalysis process toward indoor air pollutants removal VOCs.