Strong internal electric field, built in photo-active layer of thin film organic photovoltaics (OPVs), is required to efficiently extract photo-generated electrons and holes to each electrode, otherwise their recombination limits the photo-current density and consequently power conversion efficiency (PCE). Here, we report a new approach for thin film OPVs to provide large internal electric field by incorporating strong electric dipole layers (EDLs) based on p-type and n-type conjugated polyelectrolytes (CPEs) on both sides of the photo-active layer. The built-in electric field induced by p-type and n-type CPEs is significantly increased compared to that achieved by charge transport materials such as metal oxide and conducting polymer in conventional OPVs. The OPVs based on our new architecture show higher internal quantum efficiency (IQE) approaching 100%.