Information and communication technologies are transforming our daily lives in a wide variety of ways, such as the way we work, study, and interact with others. There are clear benefits to be gained from appropriate use, but a problem arises when addictive and problematic use of the Internet is experienced. In this sense, several predictive factors can be related to inappropriate or problematic Internet use. For this reason, the present study aimed to analyze whether inhibition, flexibility, emotional control (executive functions) and self-esteem directly influence all variables of problematic Internet use. Furthermore, it was examined whether executive functions, mediated by self-esteem, indirectly influence problematic Internet use. The study involved 514 university students who completed three scales, one for the assessment of problematic Internet use, one for self-esteem and one for executive functions. Mediation models showed that both executive functions and self-esteem had an influence on different problematic uses of the Internet. Specifically, it was found that flexibility and emotional control were the variables with the most direct effects, as they influenced all variables of problematic Internet use. However, when self-esteem was included as a mediator, inhibition was the variable with the most indirect effects.