Novel poly[(9,9-bis((6'-(N,N,N-trimethylammonium)hexyl)-2,7-fluorene)-alt-(9,9 -bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-9-fluorene)) dibromide (WPF-6-oxy-F) and poly[(9,9-bis((6'-(N,N,N-trimethylammonium)hexyl)-2,7-fluorene)-alt-(9,9 -bis(2-(2-methoxyethomethyl)-fluorene)] dibromide (WPF-oxy-F) compounds are developed and the use of these water-soluble polymers as an interfacial layer for low-cost poly(3-hexylthiophene):phenyl-C-61 butyric acid methyl ester (P3HT:PCBM) organic solar cells (OSCs) is investigated. When WPF-oxy-F or WPF-6-oxy-F is simply inserted between the active layer and the cathode as an interfacial dipole layer by spin-coating water-soluble polyfluorenes, the open-circuit voltage (V-oc), fill factor (FF), and power-conversion efficiency (PCE) of photovoltaic cells with high work-function metal cathodes, such as Al, Ag, Au, and Cu, dramatically increases. For example, when WPF-6-oxy-F is used with Al, Ag, Au, or Cu, regardless of the work-function of the metal cathode, the Voc is 0.64, 0.64, 0.58, and 0.63 V, respectively, approaching the original value of the P3HT:PCBM system because of the formation of large interfacial dipoles through a reduction of the metal work-function. In particular, introducing WPF-6-oxy-F into a low-cost Cu cathode dramatically enhanced the device efficiency from 0.8% to 3.36%.