Purpose To assess the predictive factors and describe the imaging features of mediastinal lymph node (MLN) metastases in patients with head and neck cancer. Materials and Methods We compared the clinical features and disease characteristics (sex, age, site of primary tumor, histologic type, history of prior treatments, TNM stages, and metastasis in cervical LNs) of patients with head and neck cancers between the MLN metastasis and no MLN metastasis groups. We also evaluated the chest CT (distribution and maximum dimension of the largest LN) and PET/CT (maximum standardized uptake value) features of MLN metastases based on the MLN classification. Results Of the 470 patients with head and neck cancer, 55 (11.7%) had MLN metastasis, involving 150 mediastinal stations. Hypopharynx cancer, recurrent tumor, T4 stage, N2/N3 stages, and M1 stage were found to be significant predicting factors for MLN metastasis. The most common location of MLN metastasis was ipsilateral station 2 (upper paratracheal LNs, 36.4%), followed by ipsilateral station 11 (interlobar LNs, 27.3%) and ipsilateral station 10 (hilar LNs, 25.5%). Conclusion Metastasis to MLNs should be considered in patients with head and neck cancer, especially in cases that are associated with a hypopharyngeal cancer, recurrent tumor, and high TNM stages.