AbstractDeveloping ultimate electromagnetic interference (EMI) shielding materials that can simultaneously upgrade the quality of generated electricity and the light‐thermal‐electric conversion efficiency based on traditional thermoelectric devices is crucially desired. Herein, a series of flexible multilayered phase change films (PCFs) is developed by a simple and novel origami strategy. The PCFs are first reported to improve the light‐thermal‐electric conversion efficiency by as high as 11.3%. Simultaneously, the PCFs could significantly upgrade the generated electricity on average voltage (27.3%), average current (23.8%), and lasting power outputs by 2010 times from microwatts to milliwatts. Besides, the EMI shielding efficiency of PCFs could be tuned from 39.2 to 71.9 dB by the origami process, the wide‐range EMI shielding performance could be suitable for varying occasions. Overall, this work provides a promising solution for both the preparation of multifunctional materials, high‐efficiency solar energy harvesting and upgrading electricity generation, which shows broad application prospects in EMI shielding, energy storage, and conversion.