The aim of this study was to determine the effect of smoking on BMI in male adolescents and explore the relationship between smoking status and diet. Methods: A cross-sectional epidemiological study into the health and diet of adolescents was carried out based on a representative sample of 375 vocational school male students aged 16–17 in the city of Chelyabinsk (Russian Federation). The students and their parents filled out verified questionnaires on their socioeconomic status, diet, and smoking status. Students’ height and body weight were measured. A comparative analysis of diets was performed between groups of smokers and non-smokers (149 and 226 individuals, respectively), and the relationship between smoking, body mass index, and actual diet was estimated. The methods used included descriptive statistics, Student’s t-test, Mann–Whitney U test, comparison of proportions, and moving average. Results: Non-smoking adolescent boys tended to have excess body mass compared with smokers (19.0% and 12.1%, respectively). Smokers (adolescent boys) consumed less meat, cereals, beans, and cheeses and more sweet beverages, added sugar, coffee, and alcohol. The bulk of the smokers’ diet was composed of carbohydrates (p = 0.026) and, to a lesser extent, proteins (p = 0.006). Conclusions: Significant differences were discovered in the diet between smokers and non-smokers (among adolescent boys), and smoking was associated with several indicators of unhealthy diet patterns. This is an important conclusion for developing a future program that could additionally protect at-risk groups of adolescents.