AbstractQuantitative structure-property relationships are of utmost importance for the rational design of materials. A systematic variation of one structure parameter in a series of polymers requires a large number of syntheses. Here combinatorial techniques are the method of choice. In this study high-throughput methods were applied for the synthesis and characterization of polymer libraries with stepwise changed composition to build up such material libraries. A high-throughput workflow was established, in which 112 different copolymerizations were performed. The polymers were characterized by means of NMR and FTIR (composition), GPC (number average molecular weight, inline imageand DSC (glass transition temperature, Tg). The gradually changed composition of the copolymers with number average molecular weights of around 150 kg ∙ mol-1 was confirmed and structure-property relationships between composition and Tgs ranging between 102 and 126 °C were proposed, rendering the polymer libraries now as a technology platform for further studies.