A theoretical model which describes the mechanism of droplet formation, structures of the complexes used in the precursor solution and hollow AgI particles prepared by the process of ultrasonic spray pyrolysis (USP) was investigated. Theoretical approaches described very well the properties of silver iodide particles collected and aged in 2-propanol after the USP process. The morphology of hollow silver iodide particles aged in 2-propanol was found to be connected with the mechanism of surface precipitation caused by low precursor density. In addition, the structures of small complexes used are directly connected with structural changes in the synthesized hollow AgI particles. The proposed model and experimental results imply that the structure of the starting thermodynamically stable AgI complexes, used for the first time as a precursor solution, affects the final particle structure. (C) 2012 Elsevier Ltd. All rights reserved.