Photovoltaic devices are essentially solar energy collectors that convert incident photons into charge carriers. However, light reflection losses and external factors (e.g., fog) can lead to an inefficient utilization of incident photons. Therefore, the development of antifogging surface materials that can efficiently reduce reflection is a critical issue in the upgradation of photovoltaic devices. Herein, inspired by the wing scale structures of butterfly Trogonoptera brookiana, an antireflective and antifogging surface (BRFS) was prepared by a method combining biotemplate and sol−gel. Remarkably, the BRFS possesses a relatively large surface roughness and exhibits superhydrophilic property (static water contact angle of 0°), which can quickly split fog droplet film within 6.6 s to realize the antifogging effect. In addition, the final transmittance of BRFS is as high as 90.25%. Furthermore, as an application demonstration, BRFS was applied to the surface of the reverse organic solar cells. Without compromising the inherent performance of the panels, the BRFS enhances the electrical performance of the inverted solar panels by 18%. This work provides a simple and effective strategy for designing surfaces with superior antifogging and antireflective properties and offers significant potential value for the practical application of photoelectric devices.