Introduction: Although previous research has highlighted the role of emotional intelligence on satisfaction at work, the underlying processes accounting for this association remain relatively unexplored. Objectives: To address this gap, this study examined the role of positive and negative affect as potential mediators in this link controlling for classic and well-known personality traits. Method: A sample of 124 Spanish secondary teachers completed an emotional intelligence scale, the positive and negative affective scale, the Big-Five questionnaire and the overall job satisfaction. Results: As expected, results showed that teachers´ EI was positively related to positive affect and negatively related to negative affect. Similarly, EI was positively associated to satisfaction at work. Besides, multiple mediation analysis revealed that EI showed a significant indirect effect (through positive affect) on satisfaction at work even when controlling for known confounding effects of gender, age, years of experience and personality traits. Conclusion: Our study contributes to understanding of mediating processes involved in increasing positive attitudes at work in teachers and suggests the implementation of intervention program in teachers designed to bolster EI abilities as a way of enhancing affect, which might increase job satisfaction.