Small-angle neutron scattering (SANS) is employed to investigate the structure and long-chain branch (LCB) content of metallocene-catalyzed polyethylene (PE). A novel scaling approach is applied to SANS data to determine the mole fraction branch content (phi(br)) of LCBs in PE. The approach also provides the average number of branch sites per chain (n(br)) and the average number of branch sites per minimum path (n(br,p)). These results yield the average branch length (z(br)) and number of inner segments n(i), giving further insight into the chain architecture. The approach elucidates the relationship between the structure and rheological properties of branched polymers. This SANS method is the sole analytic measure branch-on-branch structure and average branch length for topologically complex macromolecules.