Thermoelectric (TE) fibers are more suitable than films for portable or wearable devices. Herein, 2–3 nm thick poly (3,4‐ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) layer‐coated tellurium nanowires (PC‐Te NWs) are in situ prepared by a hydrothermal method. Then a series of PEDOT: PSS/PC‐Te NWs composite fibers are prepared by wet spinning and post‐treatment. The nanolayer prevents the agglomeration of the Te NWs and makes the NWs and PEDOT:PSS matrix have good compatibility, which results in the PC‐Te NWs content to a high value of 70 wt% and the fibers still with flexibility. The high aspect ratio of the PC‐Te NWs and the stress from the inner wall of the needle during spinning make the NWs ordered align along the composite fiber. Due to the large content and orientational arrangement of the PC‐Te NWs, as well as effective post‐treatment, an optimized composite fiber shows a power factor of 385.4 µW m−1 K−2 at 300 K, which is ≈4.9 times as high as the highest value of previously reported PEDOT:PSS/Te NWs‐based composite fibers. In addition, the composite fiber has good flexibility. The flexible TE generators assembled have excellent output performance. This work provides an effective strategy for the preparation of high‐performance flexible TE composite fibers.