We have synthesized water-soluble polymer, poly[(9,9-bis((6'-(N,N,N-trimethylammonium)hexyl)-2,7-fluorene))-alt-bisphenylfumaronitrile]dibromide (AHF-alt-PFN), the polymer typically obtained by the Suzuki type of polymerization reaction and shows good solubility in methanol. Bulk heterojunction polymer solar cells (BHJ-PSCs) fabricated by using water soluble conjugated polymer and positive (Cs+) and negative (F-, CO2-(3)) charge ions doping as an interfacial layer for poly(3-hexylthiophene):phenyl-C61 butyric acid methyl ester (P3HT:PCBM). We have achieved an enhancement of the short circuit density and power conversion efficiency in solar cell by introducing poly(AHF-alt-PFN) layer between the active layer and the cathode metal. The device with poly(AHF-alt-PRN) layer containing F-, CO2-(3) showed a short circuit current density more 1.3, 2.3 times higher than those of the device without poly(AHF-alt-PFN) + ion layer. We explain the better performance in solar cell with poly(AHF-alt-PFN) + ion layer was due not only to the increase of electron mobility in poly(AHF-alt-PFN) layer but also to the decrease of the electron barrier near cathode by the addition of the negative ions.