This study describes the bismuth vanadate thin films (BVO) as an alternative electron transport layer for widely used LiF for the electron‐only device (EODs) application. The BVO thin film is spin‐coated on a glass substrate as a function of solution concentration. The X‐ray diffraction pattern of the film deposited from 10 × 10−3m (BVO1) to 150 × 10−3m (BVO4) solution concentration possesses the BiVO4 phase with a tetragonal structure, whereas the film deposited at 200 × 10−3m (BVO5) shows the Bi2V4O11 phase with an orthorhombic structure. The surface morphology of the films confirms nanoparticle formation with the lower surface roughness. The UV–visible studies show the average transmittance of the films decreases with increasing solution concentration and the maximum average transmittance of 86% is obtained in BVO1 film. This oxygen vacancy promotes the charge transfer process very effectively. The EODs fabricated using BVO1 film (BiVO4 phase) exhibits the maximum current density of 59.2 mA cm−2 with a turn‐on voltage of 4.09 V, whereas the EOD device fabricated using BVO5 film (Bi2V4O11 phase) possesses the current density of 5.9 mA cm−2 with a turn‐on voltage of 4.09 V. Hence, the fabricated EODs using the BVO electron transport layer shows applicability in the OLED device.

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