Au nanoparticles (NPs) mixed with a majority of bone-like, rod, and cube shapes and a minority of irregu-lar spheres, which can generate a wide absorption spectrum of 400 nm–1000 nm and three localized surface plas-mon resonance peaks, respectively, at 525, 575, and 775 nm, are introduced into the hole extraction layer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) to improve optical-to-electrical conversion performances in polymer photovoltaic cells. With the doping concentration of Au NPs optimized, the cell performance is significantly improved: the short-circuit current density and power conversion efficiency of the poly(3-hexylthiophene): [6,6]-phenyl-C60-butyric acid methyl ester cell are increased by 20.54%and 21.2%, reaching 11.15 mA·cm?2 and 4.23%. The variations of optical, electrical, and morphology with the incorporation of Au NPs in the cells are analyzed in detail, and our results demonstrate that the cell performance improvement can be attributed to a synergistic reaction, including:1) both the local-ized surface plasmon resonance-and scattering-induced absorption enhancement of the active layer, 2) Au doping-induced hole transport/extraction ability enhancement, and 3) large interface roughness-induced efficient exciton dissociation and hole collection.