This study investigates how deluxe hotel employees’ perceptions of their own psychological well-being impact their job satisfaction and pro-social service behavior. It also examines the moderating effect of work–life balance on the relationship between psychological well-being and job satisfaction. A self-administered questionnaire was distributed to 275 deluxe hotel employees using convenience sampling. First, of the studied sub-factors of employee psychological well-being, positive relationships increased job satisfaction the most, followed by self-acceptance, purpose in life, and environmental mastery. Second, deluxe hotel employees’ job satisfaction positively impacted their pro-social service behavior. Third, the positive effect of one sub-factor of psychological well-being, purpose in life, had a stronger impact on job satisfaction in respondents with high levels of work–life balance. Theoretical and practical implications, as well as limitations and future research directions, are discussed.