The solid-state packing of comb-like polymers is intricately associated with the segregation process by crystallizing C16 side chains and amorphous chains. Consequently, driven by the covalent bonds between the side and main chains, this segregation manifests an alternating arrangement of amorphous and crystalline contents. By examining the crystalline content and coherent length, we concluded that the acid treatment suppresses the segregation of alkyl side chains into forming long-range order and crystalline content in the solid state. However, this effect can be reversible upon neutralization, yielding the activated sample (PEI-C16*). The decrease in the coherent length observed in PEI-C16-Cl (Figure ) can be attributed to interactions involving the chloride moiety incorporated within the polymeric structure as ammonium chloride.