Oral squamous cell carcinoma (OSCC) has a high incidence and limited prognosis, and it is of great significance to improve the prognosis by early diagnosis and accurate identification of the lesion boundaries during surgery. Polarization-sensitive optical coherence tomography (PS-OCT) can not only obtain tissue microstructure information, but also obtain tissue polarization information, which can improve the specificity of tissue diagnosis. In order to verify the feasibility of PS-OCT technology in the diagnosis of OSCC, a self-developed high-resolution PS-OCT system is used to image OSCC tissue ex vivo. The preliminary imaging results show that OSCC has an obvious birefringence effect compared with the normal tissue, and the accumulative phase retardation can be used to distinguish normal tissues and cancerous tissues. Finally, it is proved that high-resolution PS-OCT technology has great potential for identification, diagnosis, and boundary detection of OSCC tissue. In addition, it can assist surgeons in disease screening and intraoperative boundary detection.