The microstructure of pentacene thin films deposited by thermal evaporation is studied by X-ray diffraction. The transmittance of these films evidences different molecular orbital levels and their related excitonic states. Pentacene photodiodes have been also fabricated on ITO-coated glass substrates with aluminium top electrodes. The current voltage characteristics of such devices are discussed paying special attention to the strongly marked space-charge limited regime. This has been related to trapping in an exponential distribution of localised states in the gap of pentacene. The analysis of the characteristic offers valuable information about such distribution of traps. Finally, the external-quantum-efficiency of these photodiodes shows antibatic features, which evidence the importance of excitonic states in the photovoltaic conversion in pentacene.