The formation of columnar mesophases by N-acylated azacrown derivatives may be seen as a consequence of their discoid molecular geometry. Viewing these materials as cyclic oligomers, they are dust one example of the various molecular architectures that may be realized based on the N-acylated ethylenamine fragment. By using linear oligoamides, the hexagonal columnar packing is preserved, the monotropic nature of the mesophase reflecting the higher flexibility of the systems. The corresponding polymers are accessible by polymer analogous acylation of linear poly(ethylenimine), in which a high conversion of the amino groups and a low polydispersity of the final polymers can be achieved. The resulting polyamides form enantiotropic mesophases with a hexagonal columnar structure proven by polarizing microscopy, DSC investigations, and X-ray studies. A helically folded structure of the polymer main chain is proposed whereby this structural motif is probably induced by the packing of the alkyl side chains. Based on side group variations, it was found that the 3,4-bis(alkyloxy)benzoyl side group particularly matches the conformative requirements of the polymer main chain for the formation of a columnar structure. Furthermore, a hexagonal columnar mesophase was observed for a non-symmetrically substituted cinnamoyl side group. Whereas in the case of linear polymers the mesophase is stabilized at higher molecular weights,in the case of branched polyamides the enhanced degree of branching disturbs the chain packing. In the same sense, the introduction of chiral groups both in the polymer main chain and in the side-chain region disturbs the packing into an ordered columnar structure. A monotropic mesophase was found for a regularly branched oligoamide with a presumably discoid molecular structure.