Iron pyrite (FeS2) is considered a promising earth-abundant semiconductor for solar energy conversion with the potential to achieve terawatt-scale deployment. However, despite extensive efforts and progress, the solar conversion efficiency of iron pyrite remains below 3%, primarily due to a low open circuit voltage (VOC). Here we report a comprehensive investigation on {100}-faceted n-type iron pyrite single crystals to understand its puzzling low VOC. We utilized electrical transport, optical spectroscopy, surface photovoltage, photoelectrochemical measurements in aqueous and acetonitrile electrolytes, UV and X-ray photoelectron spectroscopy, and Kelvin force microscopy to characterize the bulk and surface defect states and their influence on the semiconducting properties and solar conversion efficiency of iron pyrite single crystals. These insights were used to develop a circuit model analysis for the electrochemical impedance spectroscopy that allowed a complete characterization of the bulk and surface defect states and the construction of a detailed energy band diagram for iron pyrite crystals. A holistic evaluation revealed that the high-density of intrinsic surface states cannot satisfactorily explain the low photovoltage; instead, the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a nonconstant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explaining the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings lead to suggestions to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films for successful solar applications.