Radiation-induced malignancies are a rare but serious complication arising in patients receiving radiotherapy for nasopharyngeal carcinoma (NPC). To characterize patients who develop post-irradiation squamous cell carcinoma (PISCC) of the ear after radiotherapy for NPC and to compare their outcomes with patients who have de novo squamous cell carcinoma (SCC) of the ear. Clinical and pathological characteristics and their outcomes were analysed and compared between post-irradiation and de novo SCC cases. From 2002 to 2011, 25 patients were treated at our institution for SCC of the ear, of which 8 (32%) occurred after prior irradiation. There were no significant differences between the two groups with regards to age, gender, race, smoking status, tumour size, grade, stage and differentiation. Patients in the PISCC group appeared to have inferior overall survival (median survival 71.2 vs. 85.6 months; p = 0.292) and disease-specific survival (mean 59.6 vs. 71.5 months; p = 0.441). PISSC of the ear in long-standing survivors of NPC has a poor prognosis despite advances in medical care. Surgical resection with clear margins seems to offer the best outcomes.