Triboelectric devices capable of harvesting ambient mechanical energy have attracted attention in recent years for powering biomedical devices. Typically, triboelectric energy harvesters rely on contact-generated charges between pairs of materials situated at opposite ends of the triboelectric series. However, very few biocompatible polymeric materials exist at the ‘tribopositive’ end of the triboelectric series. In order to further explore the use of triboelectric energy harvesting devices within the body, it is necessary to develop more biocompatible tribopositive materials and look into ways to improve their triboelectric performance in order to enhance the harvested power output of these devices. Poly-L-lactic acid (PLLA) is a tribopositive biocompatible polymer, frequently used in biomedical applications. Here, we present a way to improve the triboelectric output of nanostructured PLLA through fine control of its crystallinity via a customised template-assisted nanotube (NT) fabrication process. We find that PLLA NTs with higher values of crystallinity (∼41%) give rise to a threefold enhancement of the maximum triboelectric power output as compared to NTs of the same material and geometry but with lower crystallinity (∼13%). Our results thus pave the way for the production of a viable polymeric and biocompatible tribopositive material with improved power generation, for possible use in implantable triboelectric nanogenerators.