A simple, solution-processed route to the development of MoOx thin-films using oxomolybdate precursors is presented. The chemical, structural, and electronic properties of these species are characterized in detail, within solution and thin-films, using electrospray ionization mass spectrometry, grazing angle Fourier transform infrared spectroscopy, thermogravimetric analysis, atomic force microscopy, X-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy. These analyses show that under suitable deposition conditions the resulting solution processed MoOx thin-films possess the appropriate morphological and electronic properties to be suitable for use in organic electronics. This is exemplified through the fabrication of poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester (P3HT:PC61BM) bulk heterojunction (BHJ) solar cells and comparisons to the traditionally used poly(3,4-ethyldioxythiophene)/poly(styrenesulfonate) anode modifying layer.