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Objectives: Head-and-neck cancer (HNC) is a collective term for cancers of the oral cavity, paranasal sinuses, pharynx, larynx, skin, and salivary glands. HNC is the most common cancer in males and the third-most common cancer in females in India. It is associated with various psychiatric comorbidities; depression, anxiety, and substance abuse being the most common, so the study was planned to assess psychiatric comorbidities in hydrogen cyanide (HCN) patients in comparison to healthy controls. Materials and Methods: After getting approval from the institutional ethics committee, a cross-sectional study was conducted at a tertiary care center in North India. Participants recruited in the study after informed consent were of age 18 years and above, of either gender, undergoing treatment for HCN (198); their diagnosis was confirmed by histopathological examination as the study group and (140) sociodemographically matched participants as healthy controls. Participants with a history of organic brain disease, recent head trauma, or neurodegenerative disorders were excluded from the study. Sociodemographic profiles of participants were noted. For the assessment of psychiatric comorbidities, Mini-International Neuropsychiatric Interview-6 was used. The psychiatric diagnosis was confirmed by two consultants in accordance with International classifications of diseases (ICD)-10. Results: Most of the participants were males in their fifth decade. The most common psychiatric comorbidity in HCN patients was depression (27.3%), followed by adjustment disorder (14%). Tobacco was used by around half of patients with HNC, followed by alcohol use (16.1%). Conclusions: Psychiatric comorbidities were highly prevalent in HCN patients. Psychiatric disorders are known to affect both the prognosis, hospital stay, cost of treatment, and overall quality of life of cancer patients.