Fine particulate matter (PM2.5), a detrimental urban air pollutant primarily emitted by traffic and biomass burning, poses disproportionately significant health risks at relatively limited exposure during commuting. Previous studies have mainly focused on fixed locations when assessing PM2.5 exposure, while neglecting pedestrians and cyclists, who often experience higher pollution levels. In response, this research aimed to independently validate the effectiveness of bicycle-mounted low-cost sensors (LCS) adopted by citizens, evaluate temporal and spatial PM2.5 exposure, and assess associated health risks in Ljubljana, Slovenia. The LCS quality assurance results, verified by co-location field tests by air quality monitoring stations (AQMS), showed comparable outcomes with an average percentage difference of 21.29 %, attributed to humidity-induced nucleation effects. The colder months exhibited the highest air pollution levels (μ = 32.31 μg/m3) due to frequent thermal inversions and weak wind circulation, hindering vertical air mixing and the adequate dispersion of pollutants. Additionally, PM2.5 levels in all sampling periods were lowest in the afternoon (μ = 12.09 μg/m3) and highest during the night (μ = 61.00 μg/m3) when the planetary boundary layer thins, leading to the trapping of pollutants near the surface, thus significantly affecting diurnal and seasonal patterns. Analysis of exposure factors revealed that cyclists were approximately three times more exposed than pedestrians. However, the toxicological risk assessment indicated a minimal potential risk of PM2.5 exposure. The collaborative integration of data from official AQMS and LCS can enhance evidence-based policy-making processes and facilitates the realignment of effective regulatory frameworks to reduce urban air pollution. Display omitted •PM2.5 poses significant health risks at limited exposure during commuting.•Air quality monitoring stations and citizens' initiatives data integration enhances air pollution assessment.•Air quality monitoring stations co-location validation of low-cost sensors results yielded comparable outcomes.•PM2.5 increased in cold months due to thermal inversions hindering pollutant dispersion.•Cyclist had three times higher PM2.5 exposure than pedestrians.