AbstractRenewable heat‐to‐power conversion based on thermoelectric strategy holds strong prospect toward clean electricity generation in low‐carbon society, in which its conversion performance is mainly decided by the temperature gradient. However, achieving a high temperature gradient spontaneously throughout the day in natural convection remains a significant challenge. Herein, cost‐effective, sustainable, and hierarchically porous cellulose membrane (HPCM) created through a simple self‐assembly engineering of cellulose molecules is proposed. Such HPCM boasts a unique structure of layered micro‐ and nanoscaled pores with ≈95% porosity, and correspondingly demonstrates >94% solar reflectance and >0.9 mid‐infrared emissivity. As a result, HPCM enables average temperature gradient of 14.5 °C and 76 mV output voltage of thermoelectric module during daytime natural convection, which are 17‐ and 30‐time higher than those of pristine device, respectively. Note that HPCM‐based thermoelectric module consistently generates an average output voltage of 44.2 mV all day. Such modules are seamlessly integrated into thermoelectric arrays to achieve high output voltage of ≈1.5 V and power density of ≈3 W m⁻² over 90‐d period. The prepared HPCM marks a significant advancement in environmentally friendly, scalable, and viable thermoelectric conversion to power the low‐carbon society.