By hydrolyzing wheat starch solutions using different combinations of ä‐amylase and pullulanase it has been possible to achieve significantly different oligosaccharide product spectra in hydrolysates with the same dextrose equivalent (D. E.). Where pullulanase was used either as a pretreatment to α‐amolysis or in combination with α‐amylase starch hydrolysates were produced whose oligosaccharide product spectra differed significantly from the comparable hydrolysate at the same D.E. produced by α‐amylase alone. Throughout the range of starch hydrolysate D.E. values the following trends were observed: pullulanase involvement produced less G1, G2 and G5 oligosaccharides and less intermediate molecular weight fraction (D.P. > 12) than when α‐amylase alone was used. Where the D.E. values exceeded 20, in addition to these general differences, pullulanase involvement was found to be responsible for the increased production of G6 and G3 oligosaccharides and to significantly reduce the amount of unhydrolyzed polysaccharide both in the intermediate and high molecular weight fractions.