Flexible thermoelectric devices hold significant promise in wearable electronics owing to their capacity for green energy generation, temperature sensing, and comfortable wear. However, the simultaneous achievement of excellent multifunctional sensing and power generation poses a challenge in these devices. Here, ordered tellurium-based hetero-nanowire films are designed for flexible and multifunctional thermoelectric devices by optimizing the Seebeck coefficient and power factor. The obtained devices can efficiently detect both object and environment temperature, thermal conductivity, heat proximity, and airflow. In addition, combining the thermoelectric units with radiative cooling materials exhibits remarkable thermal management capabilities, preventing device overheating and avoiding degradation in power generation. Impressively, this multifunctional electronics exhibits excellent resistance in extreme low earth orbit environments. The fabrication of such thermoelectric devices provides innovative insights into multimodal sensing and energy harvesting.