The multilayer triboelectric nanogenerators (TENGs) are widely developed to enhance the output performance of device. However, these TENGs consisting of electron transfer, transport, trap layers toward a large volumetric charge density should be wearable and mass-produced for commercialization. Thus, appropriate material selection in respective layers and fabrication method are crucial for the commercialization of multilayer TENG. This study presents all-printed, sustainable wearable TENGs based on electron accumulation polymers (EAPs) with superior charge retention capability. The EAPs consisting of polytetrafluoroethylene (PTFE), carboxyl functionalized single-walled carbon nanotubes (SWCNTs:COOH), and Ti3C2Tx (MXene) in a fluorinated polymer matrix, are used. Compared to the reference, the EAPs not only lead to approximately six times higher output performance (300 V and 40 mu A) but also four times more sustainable charge retention capability (92%) for an hour. These are attributed to the three-step electron-trapping mechanism with electron transfer/transport from PTFE/SWCNT and electron trapping in MXene. In addition, TENGs with EAPs exhibit excellent mechanical stability and reliability with fascinating single-electrode demonstrations. Finally, the TENG with EAPs can efficiently operate various portable electronics and pH monitoring systems with a pH sensor and a seven-segment display in realistic scenarios.