AbstractWe describe a simple, efficient, and protecting‐group‐free, magnesium‐chloride‐promoted synthesis of nucleoside diphosphate sugars from the corresponding nucleoside 5′‐phosphorimidazolides and sugar phosphates in DMF. After optimization, nine different nucleoside sugars were synthesized and isolated in 63–92 % yield, demonstrating the applicability of this method with different nucleosides (A, G, U) and sugar moieties (1‐Glc, 6‐Glc, 1‐Gal, 5‐Rib, 1‐Fuc). The procedure worked well even when a small excess of phosphosugars over nucleotides was used, and at low reagent concentrations, which makes it useful for small‐scale (micromolar) NDP‐sugar preparations.