A series of polyhydroxyl sulfides and triazoles was prepared by reacting allyl and propargyl D-mannose derivatives with selected thiols and azides in thiol–ene and Huisgen click reactions. Conformational analysis by NMR spectroscopy proved that the intrinsic rigidity and linear conformation of the mannose derived polyol backbone is retained in the final click products in solution. Single crystal X-ray structure determination of one of the compounds prepared further verified that the linear conformation of the polyol segment is also retained in the solid state. In addition, an improved method for direct Barbier-type propargylation of unprotected D-mannose is reported. The new reaction protocol, involving tin-mediated propargylation in an acetonitrile-water mixture, provides access to multigram quantities of the desired, valuable alkyne polyol without relying on protecting group manipulations or chromatographic purification.