Ten thiophene derivatives monomers were designed based on thiophene-linker-thiophene platform and were subjected to C-Br/C-H bulk polycondensation. All of them were converted to corresponding polythiophene derivatives smoothly, indicating that up to three-building-blocks of thiophene monomers can be successfully constructed. Detailed characterizations of the obtained polymers were carried out by regular measurements, including Cyclic Voltammetry (CV), Infrared spectrum (IR), UV-Vis absorbance spectroscopy, TGA and so on. In addition, the obtained poly{phenyl-bis-(4-thiophen 2-yl-phenyl)-amine} was employed as acid sensor and the results showed that HNO3 acid could be recognized and distinguished successfully. Furthermore, a prototype monomer crystal of 2-bromo-3-(9,9-dimethyl-9H-fluoren-2-yl) thiophene is obtained and its effective reaction points distance (4.197 angstrom) is longer (37.6%) than the van der Waals radius (r(w)) of reaction points (sum of r, of bromine and hydrogen atoms 3.05 angstrom).