This paper addresses the statistics underlying cloudy sky radiative transfer (RT) by inspection of the distribution of the path lengths of solar photons. Recent studies indicate that this approach is promising, since it might reveal characteristics about the diffusion process underlying atmospheric radiative transfer (Pfeilsticker, 1999). Moreover, it uses an observable that is directly related to the atmospheric absorption and, therefore, of climatic relevance. However, these studies are based largely on the accuracy of the measurement of the photon path length distribution (PPD). This paper presents a refined analysis method based on high resolution spectroscopy of the oxygen A-band. The method is validated by Monte Carlo simulation atmospheric spectra. Additionally, a new method to measure the effective optical thickness of cloud layers, based on fitting the measured differential transmissions with a 1-dimensional (discrete ordinate) RT model, is presented. These methods are applied to measurements conducted during the cloud radar inter-comparison campaign CLARE’98, which supplied detailed cloud structure information, required for the further analysis. For some exemplary cases, measured path length distributions and optical thicknesses are presented and backed by detailed RT model calculations. For all cases, reasonable PPDs can be retrieved and the effects of the vertical cloud structure are found. The inferred cloud optical thicknesses are in agreement with liquid water path measurements.<br><br> <b>Key words. </b>Meteorology and atmospheric dynamics (radiative processes; instruments and techniques)