A Mediterranean diet (MedDiet) has emerged as a crucial dietary choice, not only in attenuating various adolescents’ metabolic health issues but it has also been associated with improved cognitive and academic achievement. However, few studies have established patterns of food consumption linked to both cognitive and academic achievement in adolescents living in a developing country with non-Mediterranean-based food. Methods: This cross-sectional study included 1296 Chilean adolescents (50% girls) aged 10–14 years. The MedDiet Quality Index was used to assess adherence to the MedDiet in children and adolescents. Through cluster analysis, four distinct dietary patterns were identified: Western diet (WD = 4.3%); low fruit and vegetables, high-sugar diet (LFV-HSD = 28.2%); low fruit and vegetables, low-sugar diet (LFV-LSD = 42.2%); and the MedDiet (25.3%). A mixed-model analysis was conducted to compare these clusters and their relationships with cognitive and academic achievements. Principal component analysis was performed to identify four primary cognitive domains: working memory, cognitive flexibility, inhibitory control, and fluid reasoning. Academic achievement was determined with five school subjects (Language, English, Mathematics, Science, and History) and included the Academic-PISA score derived from the mean scores in Language, Mathematics, and Science. Results: A marked difference was observed between the four clusters, which was mainly related to the consumption of sugar, ultra-processed foods, fruits, and vegetables. According to cognitive performance, the MedDiet group showed higher performance across all domains than the LFV-HSD, LFV-LSD, and WD groups. Regarding academic achievement, the WD underperformed in all analyses compared to the other groups, while the MedDiet was the unique profile that achieved a positive difference in all academic subjects compared to the WD and LFV-HSD groups (p < 0.05). Conclusions: These findings suggest that higher adherence to Mediterranean-style-based patterns and better food quality choices are associated with improved cognitive and academic achievements.