The aim of this study is to gain insight into how and why certain personality traits are related to experiencing burnout complaints. Drawing on insights from a stimulus-organism-response (SOR) model of personality and affect and conservation of resources (COR) theory, we specifically focus on the role of five proactive behaviors to prevent burnout (PBPBs) at work. Two research questions are addressed: (1) How are the HEXACO personality traits related to burnout complaints, and (2) to what extent do the PBPBs aimed at increasing resources act as mediators between the engagement dimensions of personality and burnout complaints. We set up a two-wave survey examining HEXACO personality, PBPBs at work, and burnout complaints in a sample of 172 employees. For our analyses we relied on multiple regression analyses and structural equation modeling. Our analyses revealed that employees high on Extraversion and Conscientiousness and low on Emotionality are less inclined to experience burnout complaints. For the trait of Conscientiousness, this could be partly explained because conscientious employees demonstrate more proactive behavior aimed at maintaining or increasing job control. Our research contributes to the burnout and personality literature as we offer insight into why specific personality dimensions are related to burnout complaints. Specific proactive behaviors aimed at increasing job resources appeared to play a small, yet relevant role in this respect, specifically for Conscientiousness. By studying the relationship between personality and behavior in association with burnout complaints, this study adds to our understanding of personalized preventive actions in the work context that can reduce burnout complaints.