Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is a highly important and attractive conducting polymer as well as commercially available in organic electronics, including electrochemical and electronic chemosensors, due to its unique features such as excellent solution-fabrication capability and miscibility, high and controllable conductivity, excellent chemical and electrochemical stability, good optical transparency and biocompatibility. In this review, we present a comprehensive overview of the recent research progress of PEDOT:PSS and its composites, and the application in electrochemical and electronic sensors for detecting liquid-phase or gaseous chemical analytes, including inorganic or organic ions, pH, humidity, hydrogen peroxide (H₂O₂), ammonia (NH₃), CO, CO₂, NO₂, and organic solvent vapors like methanol, acetone, etc. We will discuss in detail the structural, architectural and morphological optimization of PEDOT:PSS and its composites with other additives, as well as the fabrication technology of diverse sensor systems in response to a wide range of analytes in varying environments. At the end of the review will be given a perspective summary covering both the key challenges and potential solutions in the future research of PEDOT:PSS-based chemosensors, especially those in a flexible or wearable format.