In this work, one-dimensional elongated α-MoO3 structures in the form of nanobelts were synthesized by treating peroxymolybdenum solution under hydrothermal conditions. It is shown that treatment of such structures by impregnation with an aqueous sucrose solution followed by vacuum annealing at 550 °C leads to a reduction of orthorhombic MoO3 to monoclinic MoO2. At the same time, there is no carbon or carbon-containing compounds. The reduction process of the initially produced α-MoO3 is enhanced when the structures are treated with an aqueous sucrose solution under hydrothermal conditions. Moreover, the interaction of sucrose molecules with peroxymolybdenum groups under hydrothermal conditions leads to the formation of new crystallization centres and the growth of the dumbbell-like structures. In this case, a two-phase α-MoO3/MoO2 nanostructured material with two morphological particle forms is obtained. Such material design strategy could be aimed at controlling the electrochemical degradation of a high-capacity electrodes and regulating the associated deformation dynamics.