The purpose of this study was to use principal component analysis to determine the effect of meteorological elements on the concentration of PM2.5 particulate matter in Krakow, the capital of the Lesser Poland Voivodeship in southern Poland. Daily values for selected meteorological elements measured in spring, summer, autumn, and winter over a 10-year period, obtained from the Institute of Meteorology and Water Management—National Research Institute, were adopted as variables explaining PM2.5 concentrations. Data on particulate air pollution were obtained from the air monitoring station in Krakow. In spring, autumn, and winter, the first factor significantly influencing the PM2.5 concentration was the maximum, minimum, and average temperature. In summer, the average and maximum temperatures were significant. The second factor in spring was precipitation and wind speed, and the third was relative humidity. In summer, the second factor was atmospheric pressure, and the third was relative humidity. The second factor in autumn was atmospheric pressure and precipitation, and the third was relative humidity. In winter, the second factor was wind speed, and the third was precipitation and relative humidity. Throughout the study, the annual mean PM2.5 concentrations exceeded acceptable and target levels defined by the Regulation of the Minister of the Environment, and even further exceeded the level recommended by the WHO.