Since the first observation of the metal-to-insulator transition (MIT), VO2 has attracted substantial attention in terms of whether this transition is impelled by electron–phonon interaction (Peierls transition) or electron–electron interaction. Regarding Peierls transition, it has been theoretically predicted that the Fermi surface (FS) cross-section exhibits certain nesting features for a metallic phase of VO2. Various experimental studies related to the nesting feature have been reported. Nevertheless, there is no experimental result on FS topology. In this work, we determine the FS topology of the metallic phase of VO2 through studies of VO2 epitaxial thin films on TiO2(001) substrates, using synchrotron radiation angle-resolved photoemission spectroscopy (ARPES). Three electron pockets around Γ are observed in band structures along the Γ–X direction. These three bands form electron surfaces around Γ in the ΓXRZ plane. Furthermore, the lowest energy band FS exhibits the nesting feature corresponding to a nesting vector q→ = ΓR, as predicted by the calculation. Our results strongly indicate the formation of the charge-density wave with q→ = ΓR and thus, the importance of Peierls transition for the mechanism of the MIT in VO2.