The evolution in polysaccharide composition and molecular weights during sparkling wine making and aging was studied for the first time in this work. Different autochthonous grape varieties from Spain (Verdejo, Viura, Malvası́a, Albarı́n, Godello, Garnacha and Prieto Picudo) were used to elaborate sparkling wines following the champenoise method. Principal component analysis showed differentiation of wines according to polysaccharide families. This differentiation was due to the process of aging on yeast lees, but not to the variety employed. The content of mannoproteins during aging was positively correlated (r = 0.792) with total polysaccharides from grapes. After six months of aging the highest content of mannoproteins and polysaccharides rich in arabinose and galactose was obtained. Also a shift to lower molecular weights was observed. The combination of these two characteristics could imply a better foam stability and thus sensory quality of sparkling wines.