The rapid development of modern electrical engineering puts forward urgent demand for high-performance electrical insulating materials. In this study, inspired by the layered structure of natural nacre, we present a novel biomimetic composite insulating film (referred to as M/C film) that is derived from agricultural waste corncobs and industrial waste mica tailings through a sol-gel-film transformation process. The novel insulating film has excellent tensile strength (94 MPa), high dielectric strength (68 kV mm−1), low dielectric loss, good heat resistance (T0 = 235 °C), and excellent UV shielding properties. Meanwhile, the M/C film presents environmental impacts much lower than those petrochemical-based plastic film as it can be 100 % recycled in a closed-loop recycling process and easily biodegraded in the environment (lignocellulose goes back to the carbon cycle and the mica return to the geological cycle). It is a potential alternative for petrochemical plastics and provides a possible way to utilize agricultural waste and mica tailings.