Remarkably little systematic research has examined the living and working conditions for teachers in sub-Saharan Africa and how such conditions predict teacher well-being. This study assesses how various risks across several domains of teachers’ lives—measured as a cumulative risk index—predict motivation, burnout, and job dissatisfaction in the Katanga province of the Democratic Republic of the Congo. Cumulative risk is related to lower motivation and higher burnout levels, and the relationship between cumulative risk and burnout is moderated by years of teaching experience. Specifically, less experienced teachers report the highest levels of burnout regardless of their level of cumulative risk. Experienced teachers with the low cumulative risk scores report the lowest levels of burnout, and burnout increases with higher levels of cumulative risk, suggesting that burnout decreases with experience but not for teachers who experience more risk factors. Implications for research and education policy in low-income and conflict-affected countries are discussed.