Digital technology has numerous advantages for our daily lives. However, inadequate usage may lead to negative psychosocial consequences, such as anxiety and depression symptoms. Adolescents have been considered a vulnerable population since this developmental stage is usually characterized by emotionally charged situations and an increase in risk-taking and sensation seeking behavior. The aim of our study was to examine the potential protective role of emotional intelligence facets in problematic Internet and smartphone users. Participants in the study were 2197 Spanish adolescents (45.9% male, 54.1% female) with a mean age of 14.6 years old (SD = 1.65) from Malaga, Andalusia. Adolescents completed measures of emotional intelligence (WLEIS), problematic Internet use (IAT) and problematic smartphone use (SAS-SV). We conducted two separate logistic regression analyses to determine a problematic usage profile, entering age and sex as covariates, and self-emotion appraisal, other-emotion appraisal, use of emotion and emotion regulation as predictors. For problematic Internet use, our results show that older adolescents with higher other-emotion appraisal and lower use of emotion and emotion regulation are at risk of becoming problematic users. For problematic smartphone use the profile was similar, but also sex emerged as a significant predictor, that is, older female adolescents with higher other-emotion appraisal and lower use of emotion and emotion regulation are at risk of becoming problematic users. In sum, our findings may guide the design of further programs aimed at preventing adolescents’ problematic usage of digital technologies, as they point towards the specific emotional intelligence facets that problematic users need to develop.