An approach to influence and control layered superstructures by varying the methylene sequence length between two consecutive functional groups in linear precision polymers containing 2,6-diaminopyridine (DAP) groups is presented. Layered superstructures with repeating units involving three monomeric units along the chain direction with very high coherence lengths upto 110 nm are observed in case of shorter alkyl segments, (16 and 18 [Formula: see text] units), while more conventional layer superstructures incorporating only one monomer are found for related polymers with 20 [Formula: see text] units per methylene sequence. A building block model explaining the unusually large periodicity of three monomeric units is proposed wherein layers containing crystalline or amorphous methylene sequences occur in different combinations. Occurrence of different layered structures depending on crystallization conditions, methylene sequence length as well as functional group type is explained by a competition of H-interactions between the DAP groups and the van der Waal forces between the hydrophobic methylene groups.