The preparation of polythiophene derivatives with essentially 100% head-to tail (HT) couplings leads to new defect free polythiophenes. These new HT polythiophenes formed self-oriented three dimensional structure with greatly enhanced two dimensional conductivity. Presented are the synthetic method developed in our lab, the new HT-polythiophenes prepared by our method, and the preliminary physical properties of these conducting polymers, Our results show that the structure and properties of HT-substituted polythiophenes are quite sensitive to the side chains attached to the polymer's backbone.