Diet may modulate the risk of head and neck cancer (HNC) through antioxidant and anti-inflammatory effects. To date, there is limited evidence regarding the effects of the Mediterranean diet on HNC risk. The purpose of the study was to assess the association between Mediterranean diet adherence, type of diet, and vitamin C and the risk of HNC. A case–control study was conducted at the Dentistry Hospital, University of Barcelona, including 101 cases of HNC and 101 controls matched by age and sex. Dietary habits were assessed using a 14-question Mediterranean diet score that classified the type of diet into healthy diet (10–14 points), regular diet (5–9 points), and unhealthy diet (≤4 points). Multivariate logistic regression models were used to assess the association between Mediterranean diet adherence, type of diet, and vitamin C and the risk of HNC. Higher adherence to the Mediterranean diet was significantly associated with a lower risk of HNC (OR = 0.88, 95% CI: 0.79–0.98). A healthy diet (OR = 0.29, 95% CI: 0.10–0.84) and vitamin C intake (OR = 0.25, 95% CI: 0.10–0.62) were strongly associated with lower odds of HNC. Moderate egg intake was the only type of food significantly associated with a lower risk of HNC. Dietary patterns that emphasize a high intake of antioxidant and anti-inflammatory bioactive components may have a protective effect on the risk of HNC.