α,β-(1→4)-Glucans were devised as models for heparan sulfate with the simplifying assumptions that carboxyl-reduction and sulfation of heparan sulfate does not decrease the SMC antiproliferative activity and thatN-sulfates in glucosamines can be replaced byO-sulfates. The target oligo-saccharides were synthesized using maltosyl building blocks. Glycosylation of methyl 2,3,6,2′,3′,6′-hexa-O-benzyl-β-maltoside (1) with hepta-O-acetyl-α-maltosyl bromide (2) furnished tetrasaccharide3which was deprotected to α-D-Glc-(1→4)-β-D-Glc-(1→4)-α-D-Glc-(1→4)-β-D-Glc-(1→OCH3) (5) or, alternatively, converted to the tetrasaccharide glycosyl acceptor (8) with one free hydroxyl function (4‴′-OH). Further glycosylation with glucosyl or maltosyl bromide followed by deblocking gave the pentasaccharide [β-D-Glc-(1→4)-α-D-Glc-(1→4)]2-β-D-Glc-(1→OCH3) (11) and hexasaccharide [α-D-Glc-(1→4)-β-D-Glc-(1→4)2-α-D-Glc-(1→4)-β-D-Glc-(1→OCH3) (14). The protected tetrasaccharide3and hexasaccharide12were fully characterized by1H and13C NMR spectroscopy. Assignments were possible using 1D TOCSY, T-ROESY,1H,1H 2D COSY supplemented by1H-detected one-bond and multiple-bond1H,13C 2D COSY experiments.