We developed a facile technique to exfoliate centimeter-scale pristine monolayer 2D materials with near-100% exfoliation yield. The area of the exfoliated 2D single layers (MoS2 in the present case) is only limited by the dimensions of the parent bulk crystals and the size of the target substrates. The extremely high yield of the exfoliation process is possible due to the robust and uniform interaction of the metal layer with the topmost layer of the parent bulk crystal. We attribute this success to the UHV conditions, which prevent passivation of the metal surface and thus boost the strong interaction between the metal and the topmost layer of the bulk crystal. This argument was supported by the activation of forbidden phonon modes as well as softened phonon energies in the Raman spectra of monolayer MoS2 on Ag and Au metal substrates. Likewise, the Mo-S binding energy on metal substrates was reduced. A more prominent softening of phonon energies and higher intensities of the Raman forbidden modes were observed for MoS2/Ag compared to MoS2/Au, suggesting a stronger interaction of the MoS2 layers with Ag, which also resulted in more efficient exfoliation, reaching the limit the bulk crystal size. We concluded that this strong interaction between the metal and the metal substrate is non-covalent in nature. When thinned to their monolayer limit, layered materials often reveal entirely new properties compared to their bulk counterparts. Seamless integration of such diverse properties originating from different layers in a heterostructure is highly beneficial for artificial quantum matter design. However, the prospects of this field depend on the creation, manipulation, and probing of scalable single layers and their heterostructures, where state-of-the-art techniques struggle to meet the demand. Our work in this regard provides a technological breakthrough, which will open a new route to obtain large-area monolayers of MoS2 and beyond but also provide access to other fundamental properties and unique functionalities.