An analysis of psychological well-being (self-esteem and subjective vitality) of 639 Spanish university students was performed, while accounting for the amount of leisure-time physical activity. The Spanish versions of the Rosenberg Self-Esteem Scale and Subjective Vitality Scale were employed. Participants were divided into four groups (Low, Moderate, High, and Very high) depending on estimation of energy expenditure in leisure-time physical activity. Men and women having higher physical activity rated higher mean subjective vitality; however, differences in self-esteem were observed only in men, specifically between Very high and the other physical activity groups.