The vibrationally resolved anion photoelectron (PE) spectra of MoVOy-(y = 2 - 5) metal suboxide clusters are presented and analyzed in the context of density functional theory (DFT) calculations. The electronically congested spectra reflect an increase in cluster electron affinity with increasing oxidation state. Ion beam hole-burning results reveal the features in the PE spectra of MoVO2-and MoVO4- are a result of only one anion isomer, while at least two isomers contribute to electronic structure observed in the PE spectrum of MoVO3-. Spectral features of the binary systems are compared to their pure analogs, Mo2Oy and V2Oy. An attempt to characterize the anion and neutral electronic and molecular structures is made by comparison with results from DFT calculations. However, reconciliation between the cluster spectra and the calculated spectroscopic parameters is not as straightforward as in previous studies on similar systems (Yoder, B. L.; Maze, J. T.; Raghavachari, K.; Jarrold, C. C.J.. Chem. Phys. 2005, 122, 094313 and Mayhall I, N. J.; Rothgeb, D. W.; Hossain, E.; Raghavachari, K.; Jarrold, C. C. J.. Chem. Phys. 2009, 130, 124313).