The first report of star poly(L‐proline) crosslinkers is disclosed for digital light processing 3D printing of thermoresponsive hydrogels. Through chain end functionalization of star poly(L‐proline)s with methacryloyl groups, access to high‐resolution defined 3D hydrogel structures via digital light processing is achieved through photoinitiated free radical polymerization. Changing the poly(L‐proline) molecular weight has a direct influence on both thermoresponsiveness and printability, while shape‐morphing behavior can be induced thermally.