This study aimed to investigate the effect of wildfire episodes on air quality in terms of particulate matter (PM) and carbonaceous compound concentration in ambient air, and to assess deviations from typical annual patterns. The sampling was performed at a rural background site near the Adriatic coast in Croatia through 2024. To better understand contributions caused by fire events, the levels of organic carbon (OC), elemental carbon (EC), black carbon (BC), pyrolytic carbon (PyrC), optical carbon (OptC), water-soluble organic carbon (WSOC), levoglucosan (LG), mannosan (MNS), and galactosan (GA) were determined in PM₁₀ and PM_2.5 fractions (particles smaller than 10 µm and 2.5 µm, respectively). The annual mean concentrations of PM₁₀ and PM_2.5 were 14 µg/m³ and 8 µg/m³, respectively. During the fire episode, the PM_2.5 mass contribution to the total PM₁₀ mass exceeded 65%. Total carbon (TC) and OC increased by a factor of 7, EC and BC by 12, PyrC by 8, and WSOC by 12. The concentration of LG reached 1.219 μg/m³ in the PM₁₀ fractions and 0.954 μg/m³ in the PM_2.5 fractions, representing a 200-fold increase during the fire episode. Meteorological data were integrated to assess atmospheric conditions during the fire episode, and the specific ratios between fire-related compounds were analyzed.