A free‐standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface‐initiated atom transfer radical polymerization (ATRP) of 2‐hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free‐standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross‐linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross‐linking the polymer brushes. The free‐standing film thicknesses of ≈16–75 nm are controlled by simply changing the ATRP reaction time. The results show that the free‐standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.
