The detection and prevention of addictive behaviour at an early age is essential given the relationship between the age of the onset of consumption and the appearance of addiction disorders. The aim of this study was to describe the behavior related to substance use and addictive behaviors in adolescents at secondary school from 12 to 16 years of age. A cross-sectional descriptive study has been conducted. The prevalence of consumption of different addictive substances (alcohol, tobacco, cannabis, cocaine) and addictive behaviours (use of social networks and video games) were collated, and the influence of the surrounding social environment and risk perception were evaluated. The final sample was 1298 students. Alcohol, tobacco and cannabis use reflect the prevalence of last month’s consumption: 14% (11.8–15.6), 15% (13.4–17.4) and 3% (1.9–2.7) respectively. 76% of the sample frequently use the Internet (5–7 days per week). There is a positive association between the frequency of use and use in the immediate environment. The relationships found show the need for educational and preventive intervention aimed at parents and students that will allow them to know and effectively deal with possible problems associated with the consumption of addictive substances.