Polymer solar cells have several attractive features. The active materials used for fabrication devices in PSCs are soluble in most of common organic solvents, have potentials to be flexible and manufactured in a continuous printing process. In PSCs, conjugated polyelectrolytes (CPEs) are generally used for introducing interfacial dipole, and many studies focus on the modulation of interfacial dipoles by altering the side chain through the delicate design to improve their functions. The interfacial dipole between photoactive layer and electrode play an important role in modification of work function and hole blocking ability. Herein, two CPEs, PHPT and PcoPT, which have different side chains and their salts were polymerized to compare the effect of conformation, and then fabricated for polymer solar cells (PSCs).