Pure branching enzyme (Q-enzyme [(1—>4)-α-D-glucan: (1—>4)-α-D-glucan 6-glucosyltransferase, EC 2.4.1.18]) could be isolated from a crude potato tubers extract by means of a sequence of LCtechniques (HIC and IEC); Q-enzyme accepts native and synthetic non-branched (amylose-type) glucans as substrates and increased the percentage of branching by a combined hydrolytic and transfer-activity. Qenzyme accepts technical-grade potato-maltodextrin as substrate: the resulting branching patterns depend strongly on the incubation temperature. Determined molecular-level characteristics clearly show the influence of modified branching pattern on glucan-coil dimensions, conformation and interactive properties. In particular, modification of interactive characteristics on the molecular level is strongly suspected to control macroscopic/technological qualities of starch-based materials such as gelation potential or freeze/thaw-stability.