CO2-neutral power generation is considered to be one of the key cornerstones for achieving the Paris climate targets. While decentralized solutions such as wind or solar power play a major role in this, energy harvesting through contact electrification is constantly gaining interest. So-called triboelectric nanogenerators (TENG) convert random, low-frequency mechanical energy into electrical energy and can thus provide electrical energy for various applications in a decentralized manner [1]. The energy conversion can be performed at different interfaces (e.g., solid-solid, solid-liquid), which greatly expands the variety of applications. TENGs that convert energy from water droplets, such as falling raindrops, are called droplet TENGs or D-TENGs. Most D-TENGs presented in the literature are based on polytetrafluoroethylene (PTFE) or other fluorinated surfaces, which are persistent, toxic, and subject to strict regulations or bans [2, 3]. Here, we present D-TENGs based on polydimethylsiloxane (PDMS), which are considered an alternative to perfluorinated polymers. By using femtosecond laser processing, we provided the surface with microstructures, which, on the one hand, increased the contact area in the interface and, on the other hand, reduced the surface's wettability. With a static contact angle of more than 150° and a contact angle hysteresis of 3°, we could create surfaces with superhydrophobic properties. The superhydrophobicity supports the efficiency and long-term use of the D-TENGs by reducing electrical shielding and double-layer effects by preventing droplets from remaining on the D-TENG surface. At the same time, the microstructure created by the laser makes the surface less sensitive to environmental contamination, thus supporting long-term energy conversion. Laser-functionalized D-TENGs based on PDMS represent an environmentally friendly source for power generation. They could complement existing solutions, such as solar cells in dark, rainy phases or as an additional energy supply in autonomous systems (e.g., marine sensor technology).