Radiocarbon investigation of atmospheric PM2.5 aerosol synchronized with 14CO2 observations began in Debrecen in the winter of 2010. The aim of the study was to determine the contemporary and fossil carbon fractions in the aerosol and to set them against the fossil CO2 excess data referring to the same period. The mass of the collected PM2.5 mode on prebaked quartz filters was determined gravimetrically, while its total carbon mass was calculated from the pressure of CO2 gas produced after the combustion of the filters. As a result of the applied sampling and preparation method, the stable, nonvolatile carbon forms were principally studied. 14C measurements of the tiny aerosol bulk samples were performed using the EnvironMICADAS accelerator mass spectrometer at ATOMKI. The sample preparation method was tested using several blanks, standards, and real samples. Test results showed good reproducibility for the applied aerosol sample preparation and accelerator mass spectrometry (AMS) 14C analyses. Atmospheric fossil CO2 excess data were calculated according Levin et al. (2003), using the 14C results of collected CO2 samples measured by the gas proportional counting system at ATOMKI. Mass concentration of PM10 involving the PM2.5 mode in the city air exceeded the daily average of 50 μg/m3 (24-hr limit value in the EU) several times in 2011, mainly during the winter. The results showed that recently derived carbon most likely from domestic wood burning was causing the elevated carbon mass concentration of PM2.5 in Debrecen at the time. In the course of the 1-yr-long continuous and systematic comparison of fossil carbon mass concentration of PM2.5 mode and mole fraction of fossil excess of atmospheric CO2, similar and synchronous trends were observed during the studied period in Debrecen.