Three different deep eutectic solvent (DES)-based extraction procedures were rationally designed and optimized for the recovery of antioxidants from chestnut wood fiber (CWF), a clean and largely available solid waste of the tannin industry. First, a mild protocol was developed using a choline chloride (ChCl)/tartaric acid DES at 50 °C, for 90 min. Ellagic acid (EA) was identified as the only low molecular weight phenolic component of the extract. In other experiments, harsher conditions were explored involving treatment of CWF with ChCl-based DESs at 120 °C for 8 h, which afforded a solid sample characterized by high phenolic content (up to 1.0 mg of gallic acid equivalents/mg of sample) and antioxidant properties (EC50