Unique sphere-packing mesophases such as Frank-Kasper (FK) phases have emerged from the viable design of intermolecular interactions in supramolecular assemblies. Herein, a series of Cn-G2-CONH2 dendrons possessing an identical core wedge are investigated to elucidate the impact of peripheral alkyl chain lengths (Cn) on the formation of the close-packed structures. The C18 and C14 dendrons, of which the contour lengths of the periphery Lp are longer than the wedge length Lw, assemble into a uniform sphere-packing phase such as body-centred cubic (BCC), whereas the C8 dendron with short (Lp < Lw) corona environment forms the FK A15 phase. Particularly in the intermediate C12 and C10 dendrons (Lp ≈ Lw), cooling the samples from an isotropic state leads to cooling-rate-dependent phase behaviours. The C12 dendron produces two structures of hexagonal columnar and sphere-packing phases (BCC and A15), while the C10 dendron generates the A15 and σ phases by the fast- and slow-cooling processes, respectively. Our results show the impact of peripheral alkyl chain lengths on the formation of mesocrystal phases, where the energy landscape of the dendrons at Lp/Lw ≈ 1 must be more complex and delicate than those with either longer or shorter peripheral alkyl chains.