This paper examines atmospheric concentrations of particulate matter with an aerodynamic diameter smaller than 10 μm (PM₁₀) and related particle-phase toxic heavy metals Cd, Ni, and Pb during domestic heating seasons from 2010 to 2019 in Sarajevo, Bosnia and Herzegovina. In total, 242 daily PM₁₀ samples were collected using medium and high volume air samplers. The mean daily PM₁₀ mass concentration for all measurements is 75.16 μg/m³ (with the range of 28.77–149.00 μg/m³). Variation of ambient PM₁₀ was observed throughout the study in different years. Hourly values for PM₁₀ measurements during two heating seasons are also presented. Metal concentrations in PM₁₀ were analyzed by electrothermal atomic absorption spectrometry (ETAAS). Quantities of atmospheric mass concentrations of studied trace metals were observed in the following order: Pb > Ni > Cd. The mean concentrations of metals varied with Pb showing the highest concentration (ranging from 1.38 to 234.00 ng/m³), Ni ranging from 0.87 to 42.43 ng/m³, and Cd showing the lowest concentration ranging from 0.26 to 10.09 ng/m³. The concentration of Pb and Cd in PM₁₀ was strongly correlated, suggesting a common source or dependence of these metals in PM₁₀ in Sarajevo. Bioaccessibility of metals in the synthetic gastric juice was also estimated. The quantities of average bioaccessible metal fractions in PM₁₀ samples showed the following trend: Cd > Pb > Ni. The health risk assessment shows that the population of Sarajevo is at increased lifetime risk of experiencing cancer because of exposure to these Cd concentrations in PM₁₀. In addition, parallel PM₁₀ sampling on two samplers showed that obtained results are highly comparable.