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[EN] The photophysics and photochemistry of the beta-lapachone derived diphenyldihydrodioxin 3 were investigated using steady-state and time resolved techniques. Laser excitation of 3 leads to the formation of its cation radical 4 (absorption maxima at 410 and 450 nm and a lifetime of 10 mu s), which was confirmed by its thermal generation employing tris(2,4-dibromophenyl)-aminium hexachloroantimonate (BAHA) as the electron acceptor. The cation radical 4 was also formed via the triplet excited state of 3 through a triplet sensitized process using benzophenone (E-T = 69 kcal mol(-1)) as the sensitizer. ; Financial support by the Spanish Government (grant CTQ2012-32621) is gratefully acknowledged. We thank Prof. Julia Pérez-Prieto for making available the laser flash photolysis facilities at the University of Valencia. BB thanks Coordena- ção de Aperfeiçoamento do Pessoal do Ensino Superior (CAPES-Brazil) for a graduate fellowship. JCN-F thanks Generalitàt Valenciana for a Visiting Professor fellowship. ; Netto Ferreira, JC.; Lhiaubet ., VL.; Bernades, B.; Ferreira, ABB.; Miranda Alonso, MÁ. (2014). Photophysics and photochemistry of the beta-lapachone derived diphenyldihydrodioxin: generation and characterization of its cation radical. Photochemical & Photobiological Sciences. 13(12):1655-1660. https://doi.org/10.1039/C4PP00231H ; S ; 1655 ; 1660 ; 13 ; 12