The management of head and neck tumor (HNSCC) has been changing over the years, especially due to the aid of imaging techniques that help physicians to attain a correct diagnosis. These techniques represent a valuable tool to help tailor treatment and during follow-up of patients affected by malignancies. The aim of this review is to summarize the results of the most recent and relevant studies about the use of PET imaging in HNSCCs. This review is divided into six chapters: (1) The role of PET/CT in the pre-treatment phase; (2) PET/CT and radiotherapy planning; (3) PET/CT in the post-treatment setting; (4) PET/CT and SUVmax for prediction of prognosis; (5) miscellanea on the utility of PET in specific HNSCCs; (6) non-FDG PET tracers used in HNSCC. Promising results have been obtained so far. Despite the encouraging outcomes, more investigations are needed to warrant the value of this technique, especially in the pre-treatment setting.