In this paper, the mixed films with different rubrene-to-MoO₃ ratios are deposited on the substrates of Si, indium tin oxide and quartz glass by using the thermal evaporation technique. First, these films are characterized by atomic force microscopy and X-ray diffraction in order to identify their surface morphology and their structure properties. The results show that all the films are amorphous and the film has the best flatness when the rubrene-to-MoO₃ ratio is 2∶1. Second, the optical properties of the mixed films are investigated by both photoluminescence (PL) spectra and absorption spectra. The optical band gap of rubrene and MoO₃ are 2.2 eV and 3.49 eV respectively and there is almost no absorption about rubrene and MoO₃ in the near-infrared (NIR) region. However the PL spectrum shows a peak in NIR region and it indicates that the interface between rubrene and MoO₃ possesses an abrupt discontinuity at the vacuum level, resulting in electron wave functions overlapping and charge-transfer complex (CTC) forming. The intermediate state within the original band gap of rubrene with energy of 1.25 eV is induced by the CTC, which suggests the possibility of charge transfer exciton generated upon NIR excitation. The absorption spectra of the mixed films show that there is an obvious absorption. All the films have the same absorption peak except the film with a rubrene-to-MoO₃ ratio of 4∶1 and it indicates that the concentration of MoO₃ has almost no influence on the absorption of the mixed films. The optical band gaps of the mixed thin films are calculated in a spectral range of 345－1035 nm according to the Tauc equation, and the results show that the optical band gap of the film with a rubrene-to-MoO₃ ratio of 2∶1 is narrowest (~2.23 eV). In order to study the electrical characteristics of the mixed films, an Al/rubrene:MoO₃/ITO device is fabricated. The current density-voltage (J-V) characteristic is also investigated. The analysis of the J-V measurement for the device indicates that the current conduction in the Al/rubrene:MoO₃/ITO device is Ohmic type when the rubrene-to-MoO₃ ratios are 4∶1 and 2∶1, and it is Schottky type when the ratio is other value. The current for rubrene-to-MoO₃ ratio of 1∶1 is larger than that for 1∶2, which indicates that the contact is better when the surface is more smooth. These properties of the mixed films can result in the applications in the near-infrared region.