A versatile strategy is reported for the multigram synthesis of discrete oligomets from commercially available monomer. families, e.g.; acrylates, styrenics, and: siloxanes. Central to this strategy is the identification of reproducible procedures for the separation of oligomer mixtures using automated flash chromatography systems with the effectiveness :of this approach demonstrated through the multigram preparation of discrete oligomer libraries (D = 1.0). Synthetic availability, coupled with accurate, structural control, allows these functional building blocks to be harnessed for both fundamental studies as well as targeted technological applications.