An innovative biofiltration-ozonation-biofiltration process was established and applied for the treatment of oil sands process water (OSPW). With an equivalent hydraulic retention time (HRT) of 8 h, the biofiltration pretreatment removed 24.4% of classical naphthenic acids (NAs) and 3.3% of oxidized NAs from raw OSPW with removal rate of 0.4 mg/L/h and 0.1 mg/L. Oxidized NAs showed higher resistance to the biofiltration process than classical NAs. The mild ozonation process (with utilized ozone dose of 30 mg/L) removed 84.8% of classical NAs and 11.5% of oxidized NAs from the biofiltrated OSPW with a degradation efficiency of 0.3 mg classical NAs/mg O3 and 0.1 mg oxidized NAs/mg O3. However, by using the same utilized ozone dose, the degradation of classical NAs and oxidized NAs from raw OSPW was 32.1% and 3.9% with ozonation efficiency of 0.1 mg classical NAs/mg O3 and 0.0 mg oxidized NAs/mg O3, respectively. Compared with the biofiltration pretreatment, the post biofiltration process (with HRT of 8 h) showed higher degradation effect on oxidized NAs with removal ratio of 22.9% and removal rate of 0.4 mg/L/h, but showed lower degradation effect on classical NAs with removal ratio of 6.7% and removal rate of 0.0 mg/L/h. After biofiltration-ozonation-biofiltration treatment, the microbial community structure in the biofilter was investigated by next generation sequencing. Proteobacteria and Rhodococcus were dominant bacterial phyla and genus in the biofilter, the abundance of which were 47.21% and 9.50% which were different from those in raw OSPW (62.88% and 0.72%). The change of microbial community structure could be resulted from the interaction between microbial community and the circulating OSPW. The ozonation integrated biodegradation process removed 89.3% and 34.0% of classical and oxidized NAs from OSPW which shows high potential to be applied by the oil and gas industry.