Spray pyrolysis process has been used for the synthesis of non-oxide ceramic powders from liquid precursors in the Si/C/N system. Particles with a high thermal stability and with variable composition and size distribution have been obtained. In this process, the mechanisms involved in precursor decomposition and gas phase recombination of species are still unknown. The final aim of this work consists in improving the whole process comprehension by an experimental/modelling approach that helps to connect the synthesized particles characteristics to the precursor properties and process operating parameters. It includes the following steps: aerosol formation by a piezoelectric nebulizer, its transport and the chemical-physical phenomena involved in the reaction processes. This paper focuses on the aerosol characterization to understand the relationship between the liquid precursor properties and the liquid droplet diameter distribution. Liquids with properties close to the precursor of interest (hexamethyldisilazane) have been used. Experiments have been performed using a shadowgraphy technique to determine the drop size distribution of the aerosol. For all operating parameters of the nebulizer device and liquids used, bimodal droplet size distributions have been obtained. Correlations proposed in the literature for the droplet size prediction by ultrasonic nebulization were used and adapted to the specific nebulizer device used in this study, showing rather good agreement with experimental values.