The separation of an oligo(methyl acrylate) distribution, obtained from reversible addition-fragmentation chain transfer (RAFT) polymerization, in ad iscrete (dispersity = 1) oligomeric library (degree of polymerization between 1a nd 22) is presented. The properties of this library in terms of diffusivity,g lass transition temperature,a nd viscosity are determined, filling as ignificant knowledge gap associated with these materials.T he obtained oligomer library is used to construct artificial oligomer distributions on demand. These artificial oligomer distributions are used to highlight the potential to tailor physical properties of am aterial, while concomitantly demonstrating the limitations associated with size-exclusion chromatography analysis of molecular weight and dispersity in particular.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.