On-line poker is a game of chance and skill. The construct of poker playing skill has both a technical (game strategy-related) and an emotional (emotion regulation-related) aspect. A correlational on-line study (N = 354) was conducted to assess differences in technical skills and emotional characteristics related to poker playing style between experienced and inexperienced poker players. Results suggest that, with respect to emotional characteristics, experienced poker players engage in less self-rumination and more self-reflection, as compared to inexperienced players. Experienced poker players are also able to make better decisions, by mathematical standards, in a poker decision-making environment, as assessed by two fictitious on-line poker decision-making scenarios. Furthermore, this study provides supportive evidence that experienced poker players conceptualize the construct of “luck” differently from inexperienced players. A new poker playing experience scale (PES) for accurately measuring poker playing experience is presented in this paper.