In this paper we aim to understand the size/conformation relationship in waxy barley starch, a polydisperse and ultrahigh molar mass biomacromolecule. Characterizations are performed with asymmetrical flow field-flow fractionation (AsFIFFF). Furthermore, we study the effect of homogenization on the molar mass, rms radius (r(rms)) and hydrodynamic radius (r(h)). For the untreated sample, the macromolecules are elongated objects with low apparent density. As a result of homogenization, molar mass, and r(h) decrease, while rh remains unaffected. The process also induces an increase, and scaling with size, of apparent density as well as changes in conformation, represented qualitatively by r(rms)/r(h). Finally, results from AsFIFFF are compared with viscosimetry and discussed in terms of concentration and close-packing in relation to macromolecular shape and conformation. Hence, the results show that AsFIFFF and our novel methodology enable the determination of several physical properties with high relevance for the solution behavior of polydisperse macromolecules.