Incorporating nanoscale materials into suitable matrices is an effective route to produce nanocomposites with unique properties for practical applications. Due to the flexibility in precursor atomization and delivery, aerosol-assisted chemical vapour deposition (AACVD) process is a promising way to synthesize desired nanocomposite coatings incorporating with preformed nanoscale materials. The presence of nanoscale materials in AACVD process would significantly influence deposition mechanism and thus affect microstructure and properties of the nanocomposites. In the present work, inorganic fullerene-like tungsten disulfide (IF-WS2) has been codeposited with Cr2O3 coatings using AACVD. In order to understand the codeposition process for the nanocomposite coatings, chemical reactions of the precursor and the deposition mechanism have been studied. The correlation between microstructure of the nanocomposite coatings and the codeposition mechanism in the AACVD process has been investigated. The heterogeneous reaction on the surface of IF-WS2 nanoparticles, before reaching the substrate surface, is the key feature of the codeposition in the AACVD process. The agglomeration of nanoparticles in the nanocomposite coatings is also discussed.