The study tested the extent to which positive and negative affect at work mediate personality effects (EI) on job satisfaction. Participants were 523 educators who completed the Wong Law Emotional Intelligence Scale, a version of the Job Affect Scale and the General Index of Job Satisfaction. Results using structural equation modelling indicated that positive and negative affect at work substantially mediate the relationship between EI and job satisfaction with positive affect exerting a stronger influence. In males, affect at work fully mediated the EI effect on job satisfaction. Among the four EI dimensions, use of emotion and emotion regulation were significant independent predictors of affect at work. The results confirm expectations deriving from Affective Events Theory regarding the role of work affectivity as an interface between personality and work attitudes and extend the literature on EI effects in organizational settings.