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The ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering has become an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-2D heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) > 22% and has enabled single-junction PV devices to reach 25.7%, yet a fundamental understanding to how these treatments function is still generally lacking. This has established a bottleneck for maximizing beneficial improvements as no concrete selection and design rules currently exist. Here we uncover a new type of tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the > 25% PCE milestone, which is enabled by surface treating a bulk perovskite layer with hexylammonium bromide (HABr). We uncover the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient achieved through partial halide exchange that extends from defective surfaces and grain boundaries into the bulk layer. We demonstrate and directly visualize the tunability of both the 2D layer thickness, halide gradient, and band structure using a unique combination of depth-sensitive nanoscale characterization techniques. We show that the optimization of this interface can extend the charge carrier lifetime to values > 30 μs, which is the longest value reported for a direct bandgap semiconductor (GaAs, InP, CdTe) over the past 50 years. Importantly, this work reveals an entirely new strategy and knob for optimizing and tuning recombination and charge transport at semiconductor interfaces and will likely establish new frontiers in achieving the next set of perovskite device performance records.