Burnout syndrome has recently been recognized as a public health problem, widely observed in educational settings. In this study, we aimed to examine the role played by contextual variables, including job (in)stability and teachers’ personal characteristics, in predicting factors associated with teacher burnout, using a convenience sample of 137 Italian primary school teachers (94.2% female, Age: M = 47.17, SD = 8.88). The findings from the hierarchical regression analyses showed that both trait emotional intelligence (EI) and trait anxiety predicted emotional exhaustion and lack of personal accomplishment in relation to work, with EI having a negative association and anxiety having a positive association with both. As for contextual variables, job instability positively predicted low personal accomplishment, whereas teachers’ working experience predicted emotional exhaustion. We discuss these results in light of the current working environment experienced by Italian teachers, which includes a high percentage of fixed-term workers. Moreover, we examine the implications for research and interventions related to trait EI as a protective factor that might prevent the onset of chronic professional burnout among teachers and increase teachers’ effectiveness and, therefore, pupils’ well-being, resulting in positive educational outcomes.