This article investigates the feasibility of using spaceborne observations of aerosol optical thickness (AOT) derived with the Moderate Resolution Imaging Spectroradiometer (MODIS) for monitoring of fine particulate matter (PM2.5) in an environment of low aerosol loading. Previous studies of the AOT-to-PM2.5 relationship benefit from the large range of observed values. The Stockholm region features a comprehensive network of ground-based monitoring stations that generally show PM2.5 values <20 mu g m(-3). MODIS AOT at 555nm is usually <0.20 and in good agreement with ground-based sun photometer observations in this region. We use MODIS Collection 5 AOT data with a horizontal resolution of 10km x 10km and ground-based in-situ PM2.5 observations to derive an AOT-to-PM2.5 relationship that can be used to estimate fields of PM2.5. This has been carried out with respect to the months from April to September of the period 2000-2013. Relative average absolute deviations of 33-55 % (mean of 45 %) are obtained between MODIS-retrieved and ground-based PM2.5. The root mean square error is 0.2159 mu gm(-3) between retrieved and measured PM2.5. From spaceborne lidar observations, it is found that elevated aerosol layers are generally sparse in the Stockholm region. This favours remote sensing of PM2.5 from space. The deviations found between measured and retrieved PM2.5 are mainly attributed to infrequent situations of inhomogeneous aerosol layering for which column-integrated observations cannot be connected to surface conditions. Using MODIS Collection 6 data with a resolution of 3km x 3 km in a case study actually gives far fewer results than the coarser Collection 5 product. This is explained by the complex geography of the Stockholm region with a coastline and an abundance of lakes, which seems to induce biases in the retrieval of AOT at higher spatial resolution.