Wildland firefighting represents a physically and mentally demanding endeavour fraught with various risk factors. The primary aim of this study is to delineate occupational chemical exposure within the firefighting work environment on the firefront and its implications for firefighters’ health status. A systematic literature review was conducted utilising diverse keyword combinations across Scopus, Web of Science, Academic Search Complete, and ScienceDirect databases. Only English-language journal articles, real-world monitoring reports, and studies featuring samples of firefighters were considered for inclusion. Forty-one studies were analysed, with 26 focusing on firefighters’ occupational exposure to chemical agents during wildland firefighting and 15 addressing the health impairments of wildland firefighting activities. Polycyclic aromatic hydrocarbons (PAHs), VOCs, and particulates emerged as the most prevalent chemical agents in the exposure profiles of frontline firefighters. They were shown to be the main incidents of cardiovascular disease, respiratory disease, and work-related cancer. The rigorous demands of wildland firefighting have been demonstrated to significantly impact firefighter health, resulting in a notable prevalence of fatalities and illnesses. Given that an elevated number of health issues are common in this occupation, adopting advanced assessment technologies is imperative.