The miktarm star block copolymer architecture creates opportunities in both fundamental and applied research, but is often challenging to synthesize due to the requisite molecular asymmetry. In this work, we developed a new strategy to access a variety of AB₂, AB₃, and AB₄ miktoarm star polymers using identical chemistry applied to different cheap, commercially-available sugar starting materials. Monosaccharides were functionalized with initiators for atom transfer radical and ring-opening polymerization via their constituent secondary and primary alcohols, respectively. Thereafter, the orthogonal growth of poly(acrylate) and poly(lactide) blocks in two sequential reactions produced star block copolymers with excellent control over molar mass and dispersity. Small angle X-ray scattering experiments indicate these materials self-assemble into unique structures on the nanometer length scale.