Continuous measurement of hourly concentrations of 212Pb attached to aerosol particles was carried out during the whole year 2000 in the outdoor air of Milan (Italy). An improved experimental method based on on-line alpha spectroscopy during atmospheric particulate matter sampling allowed the contemporary determination of 212Pb and 214Bi through the deconvolution of the alpha energy spectral distribution analysis. The 212Pb hourly concentrations were about 100 times lower than 214Bi but showed a similar characteristic diurnal time trend. However, the influence of meteorological parameters such as rain and wind was more evident in 212Pb than in 214Bi concentrations. The 212Pb average annual concentration was 0.090 +/- 0.060 Bq/m3 with daily mean concentration varying from 0.013 to 0.333 Bq/m3.