Low glycemic index (GI) and glycemic load (GL) diets are effective for glycemic control (GC) associated with a carbohydrate-controlled meal plan. However, whether GI and GL peaks are related to GC is unknown. Objective: To compare the daily GI (DGI)/GL (DGL) and average GI (AvGI)/GL (AvGL) of meals (accounting for peaks) related to GC markers (GCM) in Brazilian adolescents. Methods: A representative national school-based (public/private) sample of students without diabetes, 12–17 years of age, was evaluated. Food intake was based on a 24 h recall. The models for complex cluster sampling were adjusted (sex, sexual maturation, age, and physical activity). Results: Of 35,737 students, 74% were from public schools, 60% girls, 17% overweight, and 8% obese. The minimum DGI and DGL were observed at lunch, with higher values at night. Fasting insulin was 1.5 times higher in overweight/obese (OW) girls, and 1.7 times higher in OW boys than in normal-weight (NW) girls. The same trend was observed for the homeostatic model assessment for insulin resistance (HOMA-IR) (OW = 2.82 vs. NW = 1.84 in girls; OW = 2.66 vs. NW = 1.54 in boys; p < 0.05). The daily and average metrics were greater for NW adolescents. Glycosylated hemoglobin was not associated with these metrics, except for AvGL. Insulin and HOMA-IR were associated with all metrics in NW adolescents, with greater coefficients associated with AvGL. Among overweight/obese adolescents, only GI metrics were associated (β = 0.23; AvGI and insulin) and appeared to have the best association with GCM. Conclusions: Among NW adolescents, GL is a better measure of carbohydrate quality, but for those with overweight/obesity, carbohydrate consumption is more associated with GC, probably because they eat/report small amounts of carbohydrates.