The paper concerns the accuracy of determining particle size distributions of the fine-grained materials by means of laser diffraction method. Selection of measuring method for determination of materials granulation depends on various properties of the sample, but mainly on the range of particle size in the sample. It must be taken into consideration that each of the measurement methods inherently generate different information about particle size distribution. The applied measurement method generates the main impact on the results of research because it uses various material properties, like: geometric properties, density or type of the surface (porosity). Influence of density and particle shape on the results of measurements by laser diffraction was studied in the paper. This method becomes a standard for measuring particle size of mineral powders. Analysis of raw materials particle size distribution was performed using a laser particle-meter Analysette 22. Investigations included measurements of particle size of raw materials characterized by various densities (coal, porphyry, barite) and the shape of the particles (copper shale ore, fly ash from coal combustion). The density of raw materials was determined by helium pycnometer, while the particle shape was expressed by coefficient which was calculated on the basis of particles geometric parameters. Geometry of the grains was measured using an optical microscope with a digital record of images by means of image analysis method. The accuracy of laser granulometric analyzes was expressed by variation coefficient of narrow particle fractions contents. Results of analyzes confirmed that the laser granulometric analysis provides accurate information about the finest particle size distribution. No significant effect of the material density on the accuracy of granulometric analysis was observed. Effect of particle shape of the tested materials caused more stable values of the variation coefficient for particles of more spherical shape what is related to the applied method of laser measurement. The accuracy of laser granulometric analyzes varies dependably on the measured particle size range of particles. The most accurate analyzed materials are these ones being the part of narrow particle fractions.