Bioinspired aerogel functionalization by surface modification and coating is in high demand for biomedical and technological applications. In this paper, we report an expedient three-step entry to all-natural surface-functionalized nanostructured aerogels based on (a) TEMPO/NaClO promoted synthesis of cellulose nanofibers (TOCNF); (b) freeze-drying for aerogel preparation; and (c) surface coating with a eumelanin thin film by ammonia-induced solid state polymerization (AISSP) of 5,6-dihydroxyindole (DHI) or 5,6-dihydroxyindole-2-carboxylic acid (DHICA) previously deposited from an organic solution. Scanning electron microscopy showed uniform deposition of the dark eumelanin coating on the template surface without affecting porosity, whereas solid state (13)C NMR and electron paramagnetic resonance (EPR) spectroscopy confirmed the eumelanin-type character of the coatings. DHI melanin coating was found to confer to TOCNF templates a potent antioxidant activity, as tested by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays as well as strong dye adsorption capacity, as tested on methylene blue. The unprecedented combination of nanostructured cellulose and eumelanin thin films disclosed herein implements an original all-natural multifunctional aerogel biomaterial realized via an innovative coating methodology.