This study aims to disentangle the factorial structure of burnout (emotional exhaustion, personal efficacy, and cynicism) and work engagement (vigor, dedication, and absorption)—two core concepts in the occupational health psychology arena. A total of 12 theoretical models were tested via confirmatory factor analysis (CFA) in a representative sample of 978 Dominican teachers. Regarding the six dimensions, the best fitting model was the one considering each factor separately. However, some correlations among these factors were extremely high. Regarding the four core dimensions, the best fitting model displayed three factors: engagement, emotional exhaustion, and cynicism. Results suggest that burnout and engagement are not two parts of a bipolar construct, but different entities. However, high correlations may lead to conceive engagement as a general factor that further contemplates the professional efficacy dimension of burnout.