This study investigates the impact of facet-engineering on the photocatalytic performance of BiVO₄ for water oxidation. The research uses photoinduced absorption spectroscopy (PIA) to analyze the charge accumulation and kinetics of holes in facet-engineered (F-BiVO₄) and non-faceted (NF-BiVO₄) BiVO₄ under operando conditions. The results show that facet-engineering significantly enhances the accumulation of long-lived holes, leading to a 30-fold increase in hole accumulation compared to NF-BiVO₄. This is attributed to the stabilization of surface holes due to band bending induced by facet engineering, which increases the lifetime of these holes. However, this energetic stabilization results in slower OER kinetics compared to NF-BiVO₄. Despite this, the increased hole density and lifetime of F-BiVO₄ lead to a 63% apparent quantum efficiency (AQE) for OER, which is 70 times higher than that of NF-BiVO₄. The study also highlights the trade-off between lifetime gain and energetic loss in facet-engineered photocatalysts, emphasizing the importance of balancing these factors to optimize photocatalytic efficiency. Additionally, the stability of F-BiVO₄ under harsh conditions is demonstrated, showing its potential for practical applications in solar-driven fuel synthesis.This study investigates the impact of facet-engineering on the photocatalytic performance of BiVO₄ for water oxidation. The research uses photoinduced absorption spectroscopy (PIA) to analyze the charge accumulation and kinetics of holes in facet-engineered (F-BiVO₄) and non-faceted (NF-BiVO₄) BiVO₄ under operando conditions. The results show that facet-engineering significantly enhances the accumulation of long-lived holes, leading to a 30-fold increase in hole accumulation compared to NF-BiVO₄. This is attributed to the stabilization of surface holes due to band bending induced by facet engineering, which increases the lifetime of these holes. However, this energetic stabilization results in slower OER kinetics compared to NF-BiVO₄. Despite this, the increased hole density and lifetime of F-BiVO₄ lead to a 63% apparent quantum efficiency (AQE) for OER, which is 70 times higher than that of NF-BiVO₄. The study also highlights the trade-off between lifetime gain and energetic loss in facet-engineered photocatalysts, emphasizing the importance of balancing these factors to optimize photocatalytic efficiency. Additionally, the stability of F-BiVO₄ under harsh conditions is demonstrated, showing its potential for practical applications in solar-driven fuel synthesis.