Complexing block copolymers with amphiphilic small molecules expands their structural diversity and offers synthetic versatility through secondary-bond interactions. In systems such as PS-b-P4VP complexed with mesogenic amphiphiles like 3-pentadecylphenol multiple factors influence the self-assembly. The small-molecule geometry, hydrogen-bond strength, and crystallization behavior are strongly affecting candidates for supramolecular self-assembly. This study investigates how the crystallization of these small molecules influences the kinetics and hierarchical structure formation in supramolecular PS-b-P4VP assemblies. We investigate the effects of small molecule loading by changing the complexing ratio (r) ranging from r=0.5 to r=2.0 to investigate the existence of different crystallization regions depending on small molecule loading. We observe that the supramolecular polymer changes its spatial arrangement to obtain a different crystal structure to avoid co-crystallization of the small molecule. This finding adds a novel design constraint that has not been discussed in crystallization-driven self-assembly of BCPs. By varying the respective chain lengths of PS and P4VP blocks while pertaining to constant parent volume fractions, we present the idea that interfacial effect between the blocks can affect the crystallization; therefore, longer chains could impose better side chain crystallization further away from the interface. The differential scanning calorimetry data implies that a change in molecular geometry can depress the melting point of the complex. This is proven when the BCP was complexed with a linear stearic acid. The steric effects brought by the molecular geometry can affect crystallization and thereby self-assembly kinetics. We also investigate the effect of phase fraction of the complexing block. Here we explore that the chain rigidity of the complexing block may disrupt the crystallization-driven self-assembly. This investigation also showcases the significance of multimodal analysis to fully understand the kinetics and thermodynamics of supramolecular self-assembly. We employ Atomic Force Microscopy (AFM) and GISAXS/ GIWAXS combined analysis to reveal the hierarchical assembly. We further emphasize the importance of predictive methods for supramolecular self-assembly and establish the groundwork for such approaches in this study. Finally, this study reveals information on the crystallization behavior of amphiphilic block copolymer complexes which are complementary to the understanding of the kinetic pathways of self-assembly of such supramolecules.