Gum Arabic is a natural acacia tree exudate containing hyperbranched polysaccharides and proteins. Here, we perform a dual chromatographic separation together with small-angle X-ray and neutron scattering structural characterizations. We show that the different species present in Gum Arabic can not be easily classified in distinct families. They are rather build from various combinations of two building blocks that are evidenced by a mismatch between small-angle X-ray and neutron scattering. One block corresponds to hyperbranched polysaccharides, which we describe as three-dimensional multi-scale porous colloids possessing three length scales of 7, 2 and 0.7 nm. The other block corresponds to protein chains that organize as Gaussian chains in solution and are prone to aggregation. A large array of polysaccharide/protein conjugates was identified, which differs in size, hydrophobicity and amino-acid content. Still, their structure is always the juxtaposition of the two building blocks structures. Additionally, small-angle neutron scattering reveals that large-scale structures are ubiquitous in Gum Arabic solutions and originate from the self-association of both free and conjugated polypeptide chains. Despite its compositional complexity, Gum Arabic solutions thus possess a robust multi-scale structure that is mainly impacted by concentration and ionic repulsions.