Despite advances in the treatment modalities, cervical cancers are one of the leading causes of cancer death among women. Pap smear and colposcopy are the existing screening methods and histopathology is the gold standard for diagnosis. However, these methods have been shown to be prone to reporting errors, which could be due to their subjective interpretation. Radiotherapy is the mainstay of treatment for the locally advanced stages of cervical cancers. The typical treatment regimen spans over 4 months, from the first fraction of radiation to clinical assessment of tumor response to radiotherapy. It is often noticed that due to intrinsic properties of tumors, patients with the same clinical stage and histological type respond differently to radiotherapy. Hence, there exists a need for the development of new methods for early diagnosis as well as for early prediction of tumor radioresponse. Optical spectroscopic methods have been shown to be potential alternatives for use in cancer diagnosis. In this review, we provide a brief background on the anatomy and histology of the uterine cervix and the etiology of cervical cancers; we briefly discuss the optical spectroscopic approach to cervical cancer diagnosis. A very brief discussion on radiation therapy and radiation resistance is also provided. We also share our experiences with the Raman spectroscopic methodologies in cervical cancer diagnosis as well as in the prediction of tumor radioresponse.