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Understanding the semiconductor-electrolyte interface in photoelectrochemical (PEC) systems is crucial for optimizing stability and reactivity. Despite the challenges in establishing reliable surface structure models during PEC cycles, this study explores the complex surface reconstructions of BiVO\(_{4}\)(010) by employing a computational workflow integrated with a state-of-the-art active learning protocol for a machine-learning interatomic potential and global optimization techniques. Within this workflow, we identified 494 unique reconstructed surface structures that surpass conventional chemical intuition-driven, bulk-truncated models. After constructing the surface Pourbaix diagram under Bi- and V-rich electrolyte conditions using density functional theory and hybrid functional calculations, we proposed structural models for the experimentally observed Bi-rich BiVO\(_{4}\) surfaces. By performing hybrid functional molecular dynamics simulations with explicit treatment of water molecules on selected reconstructed BiVO\(_{4}\)(010) surfaces, we observed spontaneous water dissociation, marking the first theoretical report of this phenomenon. Our findings demonstrate significant water dissociation on reconstructed Bi-rich surfaces, highlighting the critical role of bare and under-coordinated Bi sites (only observable in reconstructed surfaces) in driving hydration processes. Our work establishes a foundation for understanding the role of complex, reconstructed Bi surfaces in surface hydration and reactivity. Additionally, our theoretical framework for exploring surface structures and predicting reactivity in multicomponent oxides offers a precise approach to describing complex surface and interface processes in PEC systems.