The standard-of-care for the detection of laryngeal pathologies involves distinguishing suspicious lesions from surrounding healthy tissue via contrasts in colour and texture captured by white-light endoscopy. However, the technique is insufficiently sensitive and thus leads to unsatisfactory rates of false negatives. Here, we show that laryngeal lesions can be better detected in real time by taking advantage of differences in the light-polarization properties of cancer and healthy tissues. By measuring differences in polarized-light reflectance, the technique, which we named ‘surgical polarimetric endoscopy’ (SPE), generates about one-order-of-magnitude greater contrast than white-light endoscopy, and hence allows for the better discrimination of cancerous lesions, as we show with patients diagnosed with squamous cell carcinoma. Polarimetric imaging of excised and stained slices of laryngeal tissue with SPE indicated that changes in the retardance of polarized light can be largely attributed to architectural features of the tissue. We also assessed SPE to aid routine transoral laser surgery for the removal of a cancerous lesion, indicating that SPE can complement white-light endoscopy for the detection of laryngeal cancer.