Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is widely utilized as the hole transport layer (HTL) inorganic photovoltaics (OPVs) because of its low-temperature solution processing peculiarity, high optical transmittance, and excellent mechanical flexibility. However, the core-shell structure of PSS coated PEDOT results in relatively low conductivity, work function, transmittance and waterproofness of PEDOT:PSS interlayer, limiting the photovoltaic performance and stability of OPVs. Here, the conformation of PEDOT chains are regulated from helical benzoyl to linear quinon...