Combining atom transfer radical polymerization and copper-catalyzed azide-alkyne "click" chemistry, hyperbranched copolymers with uniform poly(tert-butyl acrylate-b-styrene-b-tert-butyl acrylate) triblock copolymer subchains, denoted as hyper-(PtBA-PS-PtBA)(n), were successfully prepared and characterized by size exclusion chromatography (SEC), FT-IR, and H-1 NMR. Using laser light scattering, we first studied the intrachain contraction of ultralarge hyper-(PtBA(36)-PS55-PtBA(36))(600) chains in cyclohexane, a solvent selectively poor for PS at lower temperatures. We found that at temperatures lower than 34 degrees C each PS block collapses into a small globule that was stabilized by its three neighboring PtBA blocks with no intrachain or interchain association in a dilute solution. Further, after hydrolyzing those tert-butyl (tBA) moieties into acrylic acids (AA), we comparatively studied the interchain association of linear triblock PAA(23)-PS14-PAA(23) and its resultant hyper-(PAA(23)-PS14-PAA(23))(n), with different overall molar masses in water. Our results reveal that larger hyperbranched chains have a less tendency to undergo the interchain association, and the average aggregation number (N-agg) is scaled to the weight-average degree of polycondensation [(DP)(w)], i.e., the number of linear triblock precursors inside each hyperbranched chain, as N-agg similar to (DP)(w)(-0.7). As expected, increasing salt (NaCl) concentration led to stronger interchain association, resulting in large aggregates, while linear precursors only form small polymeric micelles. Moreover, our rheological study shows, unlike their linear precursor, large hyper-(PAA(23)-PS14-PAA(23))(n) chains can form a physical gel with a network-like structure at a concentration as low as 50 g/L, whose modulus increases with (DP)(w).