We report on the large-scale synthesis of highly oriented ultrathin MoO₃ layers using a simple and low-cost atmospheric pressure, van der Waals epitaxy growth on muscovite mica substrates. By this method, we are able to synthesize high quality centimeter-scale MoO₃ crystals with thicknesses ranging from 1.4 nm (two layers) up to a few nanometers. The crystals can be easily transferred to an arbitrary substrate (such as SiO₂) by a deterministic transfer method and be extensively characterized to demonstrate the high quality of the resulting crystal. We also study the electronic band structure of the material by density functional calculations. Interestingly, the calculations demonstrate that bulk MoO₃ has a rather weak electronic interlayer interaction, and thus, it presents a monolayer-like band structure. Finally, we demonstrate the potential of this synthesis method for optoelectronic applications by fabricating large-area field-effect devices (10 μm × 110 μm in lateral dimensions) and find responsivities of 30 mA W^-1 for a laser power density of 13 mW cm^-2 in the UV region of the spectrum and also as an electron acceptor in a MoS₂-based field-effect transistor.