Five polymeric architectures with a systematic increase in architectural complexity were synthesized by "click" reactions from a toolbox of functional linear polymers and small molecule linkers. The amphiphilic architectures ranged from a simple 3-miktoarm star block copolymer to the more complex third generation dendrimer-like block copolymer, consisting of polystyrene (PSTY) and polyacrylic acid (PAA). Micellization of these architectures in water at a pH of 7 under identical ionic strength gave spherical micelles ranging in size from 9 to 30 nm. Subsequent calculations of the PSTY core density, average surface area per PAA arm on the corona-core interface, and the relative stretching of the PAA arms provided insights into the effect of architecture on the self-assembly processes. A particular trend was observed that with increased architectural complexity the hydrodynamic diameter, radius of the core in the dry state and the aggregation number also increased with the exception of the third generation dendrimer. On the basis of these observations, we postulate that thermodynamic factors controlling self-assembly were the entropic penalty of forming PSTY loops in the core counterbalanced by the reduction in repulsive forces through chain stretching. This results in a greater number of aggregating unimers and consequently larger micelle sizes. The junction points within the architecture also play an important role in controlling the self-assembly process. The G3 dendrimer showed results contradictory to the aforementioned trend. We believe that the self-assembly process of this architecture was dominated by the increased attractive forces due to stretching of the PSTY core chains to form a more compact core. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6292-6303, 2009