The fast development of the Internet of Things (IoT) has driven an increasing consumer demand for self‐powered gas sensors for real‐time data collection and autonomous responses in industries such as environmental monitoring, workplace safety, smart cities, and personal healthcare. Despite intensive research and rapid progress in the field, most reported self‐powered devices, specifically NO2 sensors for air pollution monitoring, have limited sensitivity, selectivity, and scalability. Here, a novel photovoltaic self‐powered NO2 sensor is demonstrated based on axial p–i–n homojunction InP nanowire (NW) arrays, that overcome these limitations. The optimized innovative InP NW array device is designed by numerical simulation for insights into sensing mechanisms and performance enhancement. Without a power source, this InP NW sensor achieves an 84% sensing response to 1 ppm NO2 and records a limit of detection down to the sub‐ppb level, with little dependence on the incident light intensity, even under <5% of 1 sun illumination. Based on this great environmental fidelity, the sensor is integrated into a commercial microchip interface to evaluate its performance in the context of dynamic environmental monitoring of motor vehicle exhaust. The results show that compound semiconductor nanowires can form promising self‐powered sensing platforms suitable for future mega‐scale IoT systems.