Poker playing and responsible gambling both entail the use of the executive functions (EF), which are higher-level cognitive abilities. This study investigated if online poker players of different ability showed different performances in their EF and if so, which functions were the most discriminating for their playing ability. Furthermore, it assessed if the EF performance was correlated to the quality of gambling, according to self-reported questionnaires (PGSI, SOGS, GRCS). Three poker experts evaluated anonymized poker hand history files and, then, a trained professional administered an extensive neuropsychological test battery. Data analysis determined which variables of the tests correlated with poker ability and gambling quality scores. The highest correlations between EF test results and poker ability and between EF test results and gambling quality assessment showed that mostly different clusters of executive functions characterize the profile of the strong(er) poker player and those ones of the problem gamblers (PGSI and SOGS) and the one of the cognitions related to gambling (GRCS). Taking into consideration only the variables overlapping between PGSI and SOGS, we found some key predictive factors for a more risky and harmful online poker playing: a lower performance in the emotional intelligence competences (Emotional Quotient inventory Short) and, in particular, those grouped in the Intrapersonal scale (emotional self-awareness, assertiveness, self-regard, independence and self-actualization).