A new strategy to obtain functionalized acrylate monomers is introduced using the Passerini three-component reaction (Passerini-3CR). This straightforward one-pot synthesis is characterized by excellent atom economy and structurally diverse products. By using acrylic acid and a variety of aldehydes and isocyanides, a set of several acrylate monomers was synthesized. Subsequent free radical polymerization yielded polyacrylates with tunable properties depending on the used components for the Passerini reaction. For instance, by varying the aldehyde component from acetaldehyde to heptanal, control over the glass transition in the final polymer was achieved. Moreover, for highly polar acrylate monomers a thermoresponsive behavior (upper critical solution temperature; UCST) was observed in methanol and/or ethanol.