In this research, a regioregular poly (3-alkylthiophene) derivative had been synthesized via the post-polymerization functionalization, poly (3-hexylamine thiophene), which are soluble in water and water miscible solvents such as methanol, DMSO. The suitable energy level, good thermal stability and water/alcohol solubility of polymers which promising applied in polymer solar cells and processed by water or environmental-friendly solvents. In blend of functionalization polymers and fullerene derivative potassium [6,6]-phenyl-C61-butyrate shows significant UV absorption decay phenomenon and occur precipitates follow with time increase. To further investigate the mechanism of composite, FT-IR analysis and TEM investigate were used, the polymer would be bonded with carboxyl of fullerene derivative via hydrogen bonding in the carboxyl region and TEM images demonstration the mixture that be able to self-assembly a interpenetrating network composite.