We have efficiently synthesized 36 arylopeptoid dimers with ortho‐, meta‐, and para‐substituted aromatic backbones and tert‐butyl or phenyl side chains. The dimers were synthesized by using a “submonomer method” on solid phase, by applying a simplified common set of reaction conditions. X‐ray crystallographic analysis of two of these dimers disclosed that the tert‐butyl side chain invokes a cis amide conformation with a comparatively more closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation with a more open, extended structure of the surrounding aromatic backbone.