The present study is one of the first to analyze the predictive capacity of both trait and ability Emotional Intelligence (EI) based on the Mayer and Salovey model, in relation to tobacco use in a sample of Spanish adolescents. In this study, 799 students between the ages of 12 and 16 participated. A self-report on trait EI, an EI peak performance test, and questions about habits relating to tobacco use were administered. This cross-sectional study developed a quantitative and correlation-type methodology. The main results of the regression analyses, once the sex and age of the participants were controlled, revealed negative associations between the factors of clarity and emotional repair of the trait EI with respect to the variables of tobacco use, and a positive association was found for them and emotional attention. By comparison, with respect to ability EI, emotional perception and understanding were inversely related to adolescent tobacco use. These results underscore the importance of EI skills as protective factors against early initiation and subsequent tobacco abuse.