Abstract Two-dimensional transition-metal dichalcolgenides (2D-TMDs) are among the most intriguing materials for next-generation electronic and optoelectronic devices. Albeit still at the embryonic stage, building thin films by manipulating and stacking preformed 2D nanosheets is now emerging as a practical and cost-effective bottom-up paradigm to obtain excellent electrical properties over large areas. Herein, we exploit the ultrathin morphology and outstanding solution stability of 2D WS2colloidal nanocrystals to make thin films of TMDs assembled on a millimetre scale by a layer-by-layer deposition approach. We found that a room-temperature surface treatment with a superacid, performed with the precise scope of removing the native insulating surfactants, promotes in-plane assembly of the colloidal WS2nanoflakes into stacks parallel to the substrate, along with healing of sulphur vacancies in the lattice that are detrimental to electrical conductivity. The as-obtained 2D WS2thin films, characterized by a smooth and compact morphology, feature a high planar conductivity of up to 1 μS, comparable to the values reported for epitaxially grown WS2monolayers, and enable photocurrent generation upon light irradiation over a wide range of visible to near-infrared frequencies.