Teachers’ well-being, including burnout, impacts the stress and well-being of students. Understanding the development of burnout requires not only an examination of stressors, but also a consideration of personality factors. While teachers are subject to many pressures in their profession, they have personalities that make them more or less vulnerable. Our research with 470 secondary school teachers reveals four distinct negative affectivity profiles. Our results show that negative affectivity (tendency to feel depression, anxiety, or stress) plays a role in the development of burnout. However, while teachers with a more anxious profile experience greater emotional exhaustion, those with a depressive profile have more difficulty developing a strong sense of personal accomplishment. The findings highlight the need to take into account the various facets of negative affectivity, particularly in order to be able to propose prevention and intervention approaches adapted to these specific profiles.