In recent decades, photoacoustic imaging has been used widely in biomedical research, providing molecular and functional information from biological tissues in vivo. In addition to being used for research in small animals, photoacoustic imaging has also been utilized for in vivo human studies, achieving a multispectral photoacoustic response in deep tissue. There have been several clinical trials for screening cancer patients by analyzing multispectral responses, which in turn provide metabolomic information about the underlying biological tissues. This review summarizes the methods and results of clinical photoacoustic trials available in the literature to date to classify cancerous tissues, specifically of the thyroid and breast. From the review, we can conclude that a great potential exists for photoacoustic imaging to be used as a complementary modality to improve diagnostic accuracy for suspicious tumors, thus significantly benefitting patients’ healthcare.