Transition-metal dichalcogenides like molybdenum disulphide have attracted great interest as two-dimensional materials beyond graphene due to their unique electronic and optical properties. Solution-phase processes can be a viable method for producing printable single-layer chalcogenides. Molybdenum disulphide can be exfoliated into monolayer flakes using organolithium reduction chemistry; unfortunately, the method is hampered by low yield, submicron flake size and long lithiation time. Here we report a high-yield exfoliation process using lithium, potassium and sodium naphthalenide where an intermediate ternary Li(x)MX(n) crystalline phase (X=selenium, sulphur, and so on) is produced. Using a two-step expansion and intercalation method, we produce high-quality single-layer molybdenum disulphide sheets with unprecedentedly large flake size, that is up to 400 μm(2). Single-layer dichalcogenide inks prepared by this method may be directly inkjet-printed on a wide range of substrates.