The constituent molecular structures on supramolecular assembly play an important role on multiscale spatial arrangements, properties, and functions. Especially, the simple dendron assembly provides an ideal platform for investigating how subtle molecular structural differences can affect the final lattices. Here, we demonstrate unique spherical packing phases including A15 and body-centered cubic (BCC) phases on dendron assembly, using the changes in peripheral alkyl chain lengths. The dendrons with long peripheral alkyl chains assemble into the BCC phase, while dendrons with short one in the A15 phase. At the intermediate length of the alkyl chain induced the different spherical packing structures of σ and A15 phases by different cooling protocols. Our results suggest that the alkyl chains follow the different principles of peripheral size compared to the core radius on spherical packing phases. Importantly, in the intermediate point, the pathway complexity occurs due to the different cooling protocol guides the dendron assembly forming into distinct morphologies.