Several transition-metal dichalcogenides exhibit a striking crossover from indirect to direct band gap semiconductors as they are thinned down to a single monolayer. Here, we demonstrate how an electronic structure characteristic of the isolated monolayer can be created at the surface of a bulk MoS2 crystal. This is achieved by intercalating potassium in the interlayer van der Waals gap, expanding its size while simultaneously doping electrons into the conduction band. Our angle-resolved photoemission measurements reveal resulting electron pockets centered at the K̄ and K̄′ points of the Brillouin zone, providing the first momentum-resolved measurements of how the conduction band dispersions evolve to yield an approximately direct band gap of ∼1.8 eV in quasi-freestanding monolayer MoS2. As well as validating previous theoretical proposals, this establishes a novel methodology for manipulating electronic structure in transition-metal dichalcogenides, opening a new route for the generation of large-area quasi-freestanding monolayers for future fundamental study and use in practical applications. © 2014 American Chemical Society.