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Bismuth vanadate (BiVO₄) has several electronic properties that make it a promising candidate as a photoanode for water photocatalysis; these include strong absorption across much of the visible spectrum and a conduction band edge near the hydrogen evolution potential. However, charge transport and interfacial charge transfer have been reported to be limiting factors for PEC performance. Understanding the connections between surface morphology and PEC performance remains in its nascent stages, and building an accurate structural model is key. Here, we use density functional theory calculations to study the surface morphology and electronic structure of BiVO₄, and compare them with experiment. We investigate pristine surfaces and compare with those that have defects, and discuss the implications on PEC performance.