Aerosol-assisted chemical vapor deposition (AACVD) of WOx was demonstrated using the oxo tungsten(VI) fluoroalkoxo single-source precursors, WO[OC(CF3)2CH3]4 (1) and WO[OC(CH3)2CF3]4 (2). Mechanistic studies of the decomposition of 1 and 2 were consistent with gas phase decomposition to yield tungsten (VI) dioxo intermediates during growth of WOx materials. The dioxo tungsten alkoxide precursors WO2[OC(CF3)2CH3](DME) (3) and WO2[OC(CF3)3](DME) (4) were then prepared as a means of independently generating intermediates involved in deposition of WOx materials from 1 and 2. Further experimental and computational mechanistic studies have led to synthesis of related precursors with other O-bound ligand types, including β-diketonates, β-ketoesterates, β-ketoiminates, and β-diketiminates, which have been used for deposition of WOx films and nanostructures. Similar mechanism-based design strategies using S-bound ligands have been extended to precursors for deposition of MoS2 and WS2. Precursor syntheses, mechanistic studies, deposition of films under AACVD and CVD conditions, and characterization of the resulting materials will be discussed.