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The application of molybdenum oxide in the photovoltaic field is gaining traction as this material can be deployed in doping-free heterojunction solar cells in the role of hole selective contact.For modeling-based optimization of such contact,knowledge of the molybdenum oxide defect density of states(DOS)is crucial.In this paper,we report a method to extract the defect density through nondestructive optical measures,including the contribution given by small polaron optical transitions.The presence of defects related to oxygen-vacancy and of polaron is supported by the results of our opto-electrical characterizations along with the evaluation of previous observations.As part of the study,molybdenum oxide samples have been evaluated after post-deposition thermal treatments.Quantitative results are in agreement with the result of density functional theory showing the presence of a defect band fixed at 1.1 eV below the conduction band edge of the oxide.Moreover,the distribution of defects is affected by post-deposition treatment.