The theme of well-being and discomfort at work has attracted increasing interest in recent years. The present study, according to Job Demands-Resources model (JD-R), inquires the effects of personal (optimism, internal locus of control) and organizational resources (job autonomy, supervisors and colleagues support) and general (work-to-family conflict, workload) and context specific demands (emotional dissonance) on emotional well-being and discomfort at work in call centre employees. This research was conducted through an online questionnaire, composed by measures present in scientific literature, filled out individually by call center agents (N = 507) of the same telecommunication firm. Data analysis (PASW 18) provides: descriptive statistics, correlations and multiple regressions. Personal and organizational resources improve emotional well-being at work, except for colleagues support. Optimism and supervisors support reduce emotional discomfort at work. Among organizational demands, work-family conflict and emotional dissonance increase emotional discomfort at work and, to a lesser extent, reduce the emotional well-being at work. The results, according to theoretical model, highlight the different role of demands and resources on emotional well-being and discomfort at work. The results suggest organizational politics and investments to promote emotional well-being at work, in particular training program to support emotional skills, training for supervisors, increasing job autonomy and support to work-family balance.