Polymers are commonly used to fabricate triboelectric nanogenerators (TENGs). Here, several polymer films with similar main chains but different functional groups on the side chain are employed to clarify the contributions of each functional group to contact electrification (CE). The results show that the electron‐withdrawing (EW) ability and density of these functional groups on the main chain can determine both the polarity and density of CE‐induced surface charges. Similar results are obtained for CE in both the polymer–polymer and polymer–liquid modes. A theoretical mechanism involving electron cloud overlap is proposed to explain all of these results. More importantly, the unsaturated groups on poly(tetrafluoroethylene) molecular chain are proved to have a much stronger EW ability than the saturated groups. The density of these unsaturated groups can be increased using a sputtering technique, suggesting that this is a facile and effective method of enhancing the performance of TENGs. These results clarify the correlation between the molecular structure and macroscopic electrification behavior of polymers.

Modification of polymers by ion irradiation improves their effective charge density due to the generation of electron-donating groups.

Shoes play an important role in sports and human daily life. Here, an in-shoe sensor pad (ISSP) attached to the vamp lining is based on a triboelectric nanogenerator (TENG) for monitoring the real-time stress distribution on the top side of a foot. Each sensor unit on this ISSP is an air-capsule TENG (AC-TENG) consisting of activated carbon/polyurethane (AC/PU) and microsphere array electrodes. The detection range of each AC-TENG reaches 7.27 MPa, which is enough for monitoring the pressure change during different sports. This multifunctional ISSP can realize many typical functions of conventional smart shoes, including step counting and human–machine interaction. Moreover, it can also reveal special information, including the fitness of shoes, the stress concentration on toes, and the in-motion comfort degree. The signal processing and data transmission modules in the system have a hybrid power supply with wireless power transfer, while the real-time information about feet can be observed on a cell phone. Hence, this ISSP provides a potential approach to study the feet motion and comfort degree of shoes in long-term operations, which can guide both athlete training and the customized design of shoes.