AbstractTriboelectric energy harvesting from ambient mechanical sources relies on motion‐generated surface charge transfer between materials with different electron affinities. In order to achieve highly efficient energy harvesting performance, choosing materials with a high surface charge density is crucial, and odd‐numbered polyamides (Nylons), such as Nylon‐11, are particularly promising due to their strong electron‐donating characteristics and the possibility to achieve dipolar alignment leading to high surface potential. The use of Nylon‐11 as a material for triboelectric energy harvesting has been rather limited due to the extreme processing conditions required for film fabrication, and the high‐voltage poling process required for dipole alignment. However, several methods to achieve “self‐poled” Nylon‐11 nanowires via facile nanoconfinement techniques have been demonstrated recently, leading to highly efficient Nylon‐11 nanowire‐based triboelectric nanogenerators. Here, we review the most recent advances in the fabrication of Nylon‐11 nanowires, with a focus on how nanoconfinement‐based fabrication methods can be used to control phase and crystallinity. These growth methods lead to self‐poled nanowires without the requirement for subsequent electrical poling, facilitating their integration into triboelectric energy harvesting devices. Strategies to fabricate Nylon‐11 nanowires for applications in triboelectric devices can be extended to other polymeric families as well.image