Derivatives of pentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane and methylpentacyclo [5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane were prepared from cyclopentadiene and methylcyclopentadiene by Diels-Alder reaction, [2+2] cycloaddition and carbonyl addition reaction with nitrogen-containing reagent. The products were characterized by MS, IR and ¹H NMR. The thermal decomposition properties of some compounds were studied by PDSC. Results show that the decomposition of derivatives of caged hydrocarbon is an exothermic process and the heat of decomposition increases with the pressure. The volatility of caged hydrocarbon was improved by derivatives. The results indicate that derivatives of caged hydrocarbon could be used as the components of new explosives or high energy fuels.