The combination of combinatorial techniques for the synthesis as well as for the screening of novel star-shaped block copolymers consisting of a poly(ethylene glycol) core and a poly(caprolactone) shell leads to a fast evaluation of interesting properties of these materials. The polymers could be synthesized in a fully automated parallel fashion, and the screening of their host-guest properties was accomplished by utilizing a UV/vis plate reader extraction assay. The investigated polymers revealed unimolecular micellar behavior, and their maximum loading capacity could be correlated to their chemical structure. This opens avenues to an improved understanding of the requirements for unimolecular micellar behavior. Furthermore, the accelerated findings clearly point out the advantages of applied combinatorial approaches.