The poly(3-hexylthiophene) - multiwalled carbon nanotube hybrid material (P3HT-MWCNT) was successfully prepared in the Cu(I)/DBU catalyst system via hi-situ click reaction. The properties of P3HT-MWCNT were measured by FTIR, H-1 NMR, UV-vis, XRD, TEM, SEM . The fluorescence spectrum of P3HT-MWCNT proved the covalent bond between P3HT and MWCNT, and P3HT could be coated on the surface of MWCNT. Compared with the physical blends of P3HT and MWCNT, P3HT-MWCNT prepared by click chemistry exhibited better thermal stability and a higher melting point of 243.2 degrees C. TG results also indicated that P3HT content of P3HT-MWCNT was 21.4%. It was expected to prepare novel organic-inorganic donor-acceptor hybrid material with good solubility, optical and thermal stability, which may be a promising material applied in preparation of organic photoelectron in the future.