Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is the most successful conducting polymer in terms of practical application. It possesses many unique properties, such as good film forming ability by versatile fabrication techniques, superior optical transparency in visible light range, high electrical conductivity, intrinsically high work function and good physical and chemical stability in air. PEDOT:PSS has wide applications in energy conversion and storage devices. This review summarizes its applications in organic solar cells, dye-sensitized solar cells, supercapacitors, fuel cells, thermoelectric devices and stretchable devices. Approaches to enhance the material/device performances are highlighted.