Triboelectric nanogenerator (TENG), a green energy harvester, can harvest mechanical energy from human motion to electric energy to be applied in wearable electronics and sensor network. Porous materials played an important role in enhancing electric performance of TENG. In this paper, Azobisisobutyronitrile (AIBN) is used as a self‐reactive agent to modify Polydimethylsiloxane (PDMS) to form a self‐assembled porous structure (PDMS‐N10 film) through the difference in temperature between PDMS pre‐curing and AIBN decomposition. The PDMS‐N10‐based TENG exhibits a 2.5‐fold and 2.7‐fold improvement in output voltage and current as compared with PDMS without modification respectively. In addition, 116 light‐emitting diodes could be lighted up and 22 µF capacitor is charged. The TENG is also used as a sensor or trigger device for sensing the movements of elbow, knee, wrist, or finger, which can be applied in wearable devices because of the flexibility and durability as well as low cost.