Hemoglobin plays many significant biological roles in organism. However, our knowledge about its structure and function is not enough to meet the demand of clinical diagnosis. Raman spectroscopy has been shown to be an attractive optical technique which can provide direct access to the structure and function of hemoglobin. It is a proven tool for elucidating structural information of hemes and other vicinal groups. Furthermore, it can provide a useful monitor for hemoglobin dynamics. Besides, Raman spectroscopy has notable advantages in the fields of abnormal hemoglobin diagnosis, hemoglobin oxygen saturation determination and blood methemoglobin analysis. The present paper reviews the research on hemoglobin structure and function using Raman spectroscopy and the application in hemoglobinopathy diagnosis. In addition, we discuss the factors affecting the measurement in Raman spectroscopy of hemoglobin. The aim of the review is to promote the application of Raman spectroscopy to the research of hemoglobin structure and function.