In recent years, the mode of alcoholic intake known as binge drinking (BD) has become a common practice, especially among adolescents who, due to socio-environmental motives, tend to reach a rapid state of drunkenness. This drunkeness leads to alterations in brain areas responsible for executive functions and cognitive processes, as well as to the genesis of factors that predispose to lasting addiction. Likewise, nicotine leads to a comparable degree of addiction. On this basis, the aim of this research was to evaluate, on a cohort of 349 high school students (15–17 years old) in the province of Palermo, the following: (I) the drinking model of alcoholic beverages; (II) the use of nicotine and the degree of dependence; (III) the correlation between the consumption of alcoholic beverages and the use of nicotine. We employed the AUDIT-C test and the Fagerström test, two valid and standard instruments, in order to assess alcohol and nicotine use, respectively. Statistical analysis of the data showed that male and female students consumed alcohol prominently in a BD mode (77.2%, audit score (AS) 3.497, confidence interval (CI) 3.206–3.788; 69.6%, AS 2.793, CI 2.412–3.274) and nicotine (41.5%, Fagerström score (FS) 3.882, CI 3.519–4.245; 28%, FS 3.286, CI 2.547–4.024). Furthermore, a positive correlation between alcohol consumption and nicotine use was found for male (r = 0.6798, p < 0.0001) and female (r = 0.6572, p < 0.0001) students. This study provided further insights into the use of legal substances of abuse in adolescents, evidencing the obvious need for the promotion of specific school educational programs aimed at the wellbeing of youth populations.