The density functional theory (DFT) with the MPW3PBE functionality is used to optimize the firefly keto-form oxyluciferin with the substitution of methyl, methoxy, cyano, fluoride, amino and nitro groups. Based on the optimized molecular structures, the ionization potentials (IP), electron affinities (EA), hole extraction potentials (HEP), electron extraction potentials (EEP), as well as the hole and electron reorganization energy (λ) are calculated to investigate the hole and electron transport properties. The electronic absorption spectra, the lowest excited singlet state S1 and the fluorescence spectra of firefly keto-form oxyluciferin derivatives are calculated by the time dependent density functional theory (TDDFT) MPW3PBE/6-31+G(d) method. The results show that KNH2 can be used as hole-transport materials, KNO2, KCN, KF, KOCH3, KNH2 and KCH3 can be used as electron transport materials.