It is well established that gas/humidity-sensing properties of spinels are markedly influenced by their stoichiometry and microstructure. In this work nucleation and spinel phase development in the Zn-Cr-O system were investigated from the viewpoint of structural and morphological phenomena occurred during nanophased particle synthesis through aerosol reaction. The aerosol was generated from nitrates precursor solution using ultrasonic atomizer operated at 1.7 MHz. The influence of different decomposition schedules on the particle chemical content and morphology was determined by adjusting the processing parameters (aerosol droplet density 3.9x10⁶ droplets/cm³, droplet velocity 0.035m/s, max. temperature 900^oC and residence times 3, 6 and 9s). A composite particle structure comprised of primary crystallites sized from 22 to 44nm is revealed by SEM and TEM analysis. XRD structural analysis (crystallite size, microstrains, unit cell and ionic occupancies) is performed in accordance with procedure based on Koalariet-Xfit program. A certain degree of non-stochiometry is characteristic for all powders. Homogenous distribution of the constituting elements and Zn/Cr ratio of about 0.68 are proved by EDAX mapping analysis in 470nm sized as-prepared particles. After additional treatment at 1000^oC octahedral crystals form with the (111) surface dominat. Evaluated spinel non-stochiometry (Zn/Cr=0.58) is a result of the ZnO dissolving (1.9%wt) in the stoichiometric ZnCr₂O₄. Determination of the way by which the ZnO is incorporated into the spinel lattice is performed according to the procedure based on calculation of both formation and attachment energies.