We report the derivatization of hyperbranched poly(acrylic acid) (PAA) films with a wide range of amino- or alcohol-terminated molecules. These molecules can include moieties such as pyrene, ferrocene, poly(ethylene glycol), 15-crown-5, and a dye. To derivatize PAA films, we activate their carboxylic acid groups with isobutyl chloroformate and allow them to react with amine- or alcohol-containing molecules. Infrared spectroscopy demonstrates the formation of amide and ester bonds upon coupling as well as the presence of the derivative functional groups. Excimer fluorescence from pyrene-containing films implies a high density of pyrene groups. However, we can control the amount of pyrene in the film (and obtain monomer fluorescence) by varying the concentration of Py(CH2)3CONH(CH2)2NH2 in the derivatization solution. Cyclic voltammetry of ferrocene-containing films shows an electrochemically addressable ferrocenyl surface coverage of (6 ± 3) × 10-9 mol/cm2 in three-layer PAA films. PAA films and their deri...