The synthesis of copolymers containing thiophene and benzimidazole unit by Stille polymerization is reported. The polymers with many unsubstituted thiophene units in the backbone have been reported to show low solubility, which has been a problem for spin-coating for the device fabrication. In dihexyl-2H-benzimidazole, the sulfur at 2-position of BT unit was replaced with dialkyl substituted carbon, while keeping the 1,2-quinoid form, to improve the solubility of the polymers. The PL emission spectra of the PHBIT1, PHBIT2 and PHBIT3 in chloroform solutions show maximum peaks at 500~561 nm. In thin films, maximum peaks of the PHBITs appeared at 529, 562 and 569 nm, respectively. The EL emission maxima of the PHBIT1 and PHBIT2 appear at around 588 and 576 nm, respectively. The current density and maximum luminescence of the LED with the configuration of ITO/PEDOT/ PHBIT2/Ca/Al are 552 mA/$cm^2$ and 46 cd/$m^2$, respectively.