The opportunity to use one’s skills at work is an important prerequisite for employee well-being. Drawing on self-determination and person-environment fit theory, this study aims to add to our understanding of this important phenomenon in two ways. First, we examine the associations of within-subject daily variations in skill utilization and well-being. Second, we model work value orientation as a between-subject factor that moderates this within-subject relationship. Specifically, we advocate that daily skill utilization is more beneficial (in terms of more daily work engagement and less daily emotional exhaustion) for employees holding predominantly intrinsic (i.e., self-development, community contribution) as opposed to extrinsic (i.e., financial success, status) values. Results of multilevel modeling using diary data from 99 service workers over five working days, supported the assumption that daily skill utilization was positively related to daily work engagement, particularly among employees holding a predominantly intrinsic work value orientation. Contrary to expectations, daily skill utilization was unrelated to daily exhaustion, both for employees holding high and low intrinsic values. The discussion highlights the importance of, and employees’ receptiveness to, variations in beneficial working conditions.