In patients with head and neck cancer, conventional anatomical magnetic resonance imaging (MRI) scans are commonly used for identification of primary lesion, assessment of structural distortion, and presence of metastatic lymph nodes. However, quantitative analysis of diffusion MRI can provide added value to structural and anatomical evaluation of head and neck tumors (HNT), by differentiation of primary malignant process, prognostic prediction, and treatment monitoring. In this article, we will review the applications of quantitative diffusion MRI in identification of primary malignant tissue, differentiation of tumor pathology, prediction of molecular phenotype, monitoring of treatment response, and evaluation of posttreatment changes in patient with HNT.