Photodynamic therapy (PDT) as an alternative choice of cancer treatment method has attracted increasing attention in the past few decades. A sufficient amount of oxygen is essential for the production of singlet oxygen (1O2) in successful PDT; however, hypoxia is a typical hallmark of cancer, which is one of the most important limitation factors of PDT. To overcome the hypoxic tumour microenvironment and achieve highly efficient photodynamic cancer therapy, herein, a photosensitizer Ce6-loaded fluorinated polymeric micelle (Ce6-PFOC-PEI-M) was constructed via the self-assembly of an amphiphilic polymer prepared from perfluorooctanoic acid and branched polyethyleneimine (10 kDa). The introduction of perfluoroalkyl groups in the polymeric micelle Ce6-PFOC-PEI-M retained the oxygen-carrying capacity similar to perfluorocarbon, increased the oxygen level and overcame the hypoxia in C6 glioma cells under oxygen-deficient conditions. As a control, Ce6-OC-PEI-M without a perfluoroalkyl group could not increase the oxygen level in C6 glioma cells under the same conditions. With laser irradiation, Ce6-PFOC-PEI-M generated much more reactive oxygen species (ROS) in C6 glioma cells than Ce6-OC-PEI-M, leading to a higher phototoxicity in vitro and photodynamic tumour growth inhibition in vivo than Ce6-OC-PEI-M. Furthermore, there were no differences in the contents of Ce6 in tumour tissue between Ce6-PFOC-PEI-M and Ce6-OC-PEI-M. The higher efficacy of Ce6-PFOC-PEI-M in PDT is ascribed to its oxygen-carrying ability rather than higher content of Ce6 in the tumour. The presented fluorinated polymeric micelle could provide a new platform in the delivery of various photosensitizers and has great potential to improve the efficacy of PDT cancer therapy.