Oral cancer is the most common malignant tumor in the oral and maxillofacial region, which seriously threatens the health of patients. At present, radiotherapy is one of the commonly used methods for oral cancer treatment. However, the resistance of cancerous tissues to ionizing radiation, as well as the side effects of X-rays on healthy tissues, still limit the application of radiotherapy. Therefore, how to effectively solve the above problems is still a challenge at present. Generally speaking, elements with high atomic numbers, such as bismuth, tungsten, and iodine, have a high X-ray attenuation capacity. Using nanomaterials containing these elements as radiosensitizers can greatly improve the radiotherapy effect. At the same time, the modification of nanomaterials based on the above elements with the biocompatible polymer can effectively reduce the side effects of radiosensitizers, providing a new method for the realization of efficient and safe radiotherapy for oral cancer. In this work, we prepared Tween-20-modified BiVO 4 nanorods (Tw20-BiVO 4 NRs) and further used them in the radiotherapy of human tongue squamous cell carcinoma. Tw20-BiVO 4 NRs are promising radiosensitizers, which can generate a large number of free radicals under X-rays, leading to the damage of cancer cells and thus playing a role in tumor therapy. In cell experiments, radiotherapy sensitization of Tw20-BiVO 4 NRs significantly enhanced the production of free radicals in oral cancer cells, aggravated the destruction of chromosomes, and improved the therapeutic effect of radiotherapy. In animal experiments, the strong X-ray absorption ability of Tw20-BiVO 4 NRs makes them effective contrast agents in computed tomography (CT) imaging. After the tumors are located by CT imaging, it helps to apply precise radiotherapy; the growth of subcutaneous tumors in nude mice was significantly inhibited, confirming the remarkable effect of CT imaging-guided radiotherapy.