Multicomponent oxides are of increasing interest for electrochromic electrodes. To reduce the large number of permutations in composition it would be useful to be able to predict the properties of the mixtures from the pure oxide components. WO3 mixed with V2O5 has been produced by a sol-gel technique in order to increase durability and color neutrality of conventional WO3 electrochromic coatings. Chemical composition was confirmed by Rutherford backscattering spectrometry (RBS). Surface morphology was analyzed by atomic force microscopy (AFM). Electrochromic performance of the films was tested by cyclic voltammetry with in-situ transmission control. Optical constants of vanadium tungsten oxides were determined over the whole solar spectrum. The measurements included variable angle spectroscopic ellipsometry and spectral transmittance and reflectance. An attempt is made to treat doped tungsten oxide as an effective medium consisting of a mixture of WO3 with V2O5. In the clear state, comparison of optical constants and thickness directly determined on the samples yields qualitative agreement with results from effective-medium analysis. The resulting component fraction also agrees as long as the film density does not deviate too much from the linearly interpolated value between the pure components. For the colored state, preferential trapping of electrons at one atom species hinders the application of effective medium theory.