The properties and reactivity of the 9-xanthyl radical (X-center dot) in the doublet excited state (X-center dot(D-1)) were investigated using nanosecond-picosecond two-color two-laser flash photolysis. The absorption and fluorescence spectra of X-center dot(D-1) were observed for the first time. The reactivity of X-center dot(D-1) toward a series of halogen donors and electron acceptors in acetonitrile and 1,2-dichloroethane (DCE) was investigated. It is confirmed that X-center dot(D-1) has a halogen abstraction ability from a series of halogen donors. On the basis of the solvent effect on the quenching rate constants of X-center dot(D-1), an electron transfer from X-center dot(D-1) to CCl4 was indicated.