Crystalline catalysts of orthorhombic MoO3 have been prepared via a vapor phase deposition method, and their crystallographic structure has been affirmed by XRD and FTIR investigations. A chemical etching method has been developed for restructuring these thermally processed catalysts. Using a 0.1 M NaOH etchant, {001} and {100} plane areas of the catalysts can be significantly increased while surface steps, ledges, and terraces are created. Moreover, alternate crystal plane combinations of either {100} and {010} or the {001} and {010} are observed on crystal edges and rectangular etch pits in the basal planes {010}. Both materials chemistry of MoO3 and etching mechanisms have been studied on the basis of the surface morphological evolution of etching patterns of the catalysts. Technological merits and the processing parameters of this new method have also been identified. Following the findings of the current work, it is believed that the chemically carved surface structures may be crucial for certain MoO3-involving catalytic reactions.