Rapid assembly of starch fragment analogues was achieved using "click chemistry". Specifically, two hexadecasaccharide mimics containing two parallel maltoheptaosyl chains linked via [1,2,3]-triazoles to a maltose core were synthesized using Cu(i)-catalyzed [3 + 2] dipolar cycloaddition of azido saccharides and 6,6'- and 4',6'-dipropargylated p-methoxyphenyl maltoside.