Indoor photovoltaics (IPVs) using low‐toxicity bismuth‐based perovskite‐inspired materials (PIMs) can potentially power the growing number of Internet of Things devices sustainably. However, modest indoor power conversion efficiency (PCE) values are reported due to intrinsic limitations of PIMs, particularly regarding charge carrier separation and transport. Herein, polycrystalline Cs₂AgBi₂I₉ thin films are developed with high phase purity and study their fundamental structural and photophysical properties. The comprehensive experimental and computational study reveals unique optoelectronic properties of Cs₂AgBi₂I₉ compared to other bismuth‐containing PIMs, including weak electron‐phonon coupling and low exciton binding energy (40 meV). This study also demonstrates the feasibility of large and highly mobile polaron formation in Cs₂AgBi₂I₉, supported by the observation of a phonon bottleneck and a delayed hot carrier lifetime of over 200 ps, which suggests enhanced defect tolerance and transport properties. Motivated by the suitable bandgap of this absorber (1.78 eV), the first Cs₂AgBi₂I₉‐based IPVs are developed, achieving a PCE of ≈8% at 1000 lux. Notably, the devices maintain high performance across various indoor environments with white LED color temperatures ranging from 2700 to 6500 K. The calculated theoretical PCE limit of >40% and the promising operational stability position Cs₂AgBi₂I₉ as one of the most intriguing candidates for sustainable IPVs.