Alkynyldextrans with a DS in the range 0.1–1.67 have been prepared as reactive intermediates for further polymer-analogous functionalisation. DS and substituent distribution were determined by GLC and GLCMS after hydrolysis and acetylation, or methanolysis and trimethylsilylation. Reactivity was in the order O-2 > O-4 ≥ O-3 with pronounced differences in the distinct patterns for propargyl ethers and its higher homologous. A large deviation from a random substituent distribution was observed. Propargyldextrans were not stable during long-time storage in the solid state, while terminal pentynyl and hexynyl ethers are. Pentynyldextrans showed structure formation of various geometries. They bound silver efficiently, yielding silver nanoparticles by reduction.