Air pollution is recognized as a critical global health risk, yet there has been no comprehensive assessment of its impact on public health in Libya until now. This study evaluates the burden of disease associated with ambient particulate matter (PM2.5) in Libya, drawing on data from the Global Burden of Disease Study 2019. By integrating satellite-based estimates, chemical transport models, and ground-level measurements, PM2.5 exposure and its effects on mortality and disability-adjusted life years (DALYs) across the different sexes and all age groups from 1990 to 2019 are estimated. Our findings reveal that the annual population-weighted mean PM2.5 concentration in Libya was 38.6 μg/m3 in 2019, marking a 3% increase since 1990. In the same year, PM2.5 was responsible for approximately 3368 deaths, accounting for 11% of all annual deaths in the country. Moreover, a total of 107,207 DALYs were attributable to PM2.5, with ischemic heart disease being the leading cause, representing 46% of these DALYs. The analysis also highlights a significant burden of years of life lost (YLLs) at 89,113 and years lived with disability (YLDs) at 18,094, due to PM2.5. Given the substantial health risks associated with air pollution, particularly from ambient particulate matter, Libyan authorities must implement effective policies aimed at reducing air pollution to enhance healthcare outcomes and preventive services.