The soluble bis(fluoroalkOxide) dioxo tungsten(VI) complexes WO2(OR)(2)(DME) [1,R = C(CF3)(2)CH3; 2, R = C(CF3)(3)] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The H-1 NMR and F-19 NMR spectra of 1 and 2 are consi$tent with an equilibrium between the dimethoxyetharie (DME) complexes 1 and 2 and the solvato complexes WO2(OR)(2)(CD3CN)(2) [1b, R = C(CF3)(2)CH3; 2b, R = C(CF3)(3)] in acetonitrile-d(3) solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and therrnolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimetization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 degrees C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work fuhction (4.9-5.6 eV), mean optital transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.