Cyclopentadiene was prepared from its dimeric form by pyrolysis at 200 ℃. By using cyclopentadiene and 1, 4-benzoquinone as starting materials, pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane was synthesized with total yield 51.6% via Diels-Alder, [2+2]photo-cycloaddition and Huang-Minlong reduction. The products were characterized by ¹H NMR, ¹³C NMR, IR spectra and MS. The optimal conditions of Diels-Alder and [2+2]photo-cycloaddition were discussed and confirmed. The optimum conditions for Diels-Alder reaction are: the reaction temperature of dropwise is -11 ℃, the reaction time 3 h. The best condition of [2+2]photo-cycloaddition are as following: the acetone as solvent, the raw materials concentration is 2 g·125mL^-1 and the reaction time 23 h.