Copolymer, regiorandom and regioregular poly ( 3-octylthiophene )-co-poly ( 3-( 2-ethyl-1- hexylthiophene))(P3OTIOT) was synthesized by a FeCl3-oxidation and GRIM (grignard method) approach. The structure and optical properties were verified by the Fourier transform infrared, ultraviolet visible spectroscopy, NMR (nuclear magnetic resonance ), gel permeation chromatography (GPC) and photoluminescence (PL). The results indicate that the band-gap energy of the regioregular HT P3OTEHT was lower than that of the regiorandom copolymer and both of them depict low band-gap energy, high photoluminescence quantum yield, excellent solubility and processability, and might be promising polymer materials for applications in polymer light-emitting diodes, light-emitting electrochemical cells and polymer solar cells, etc.