Cocoa bean shell (CBS) waste is obtained in large amounts in chocolate production. In this work, microwave-assisted extraction (MAE) of CBS was used and experimental parameters were optimised by using response surface methodology. Effects of pH, time, temperature and solid:liquid ratio were evaluated on the extraction yield, total uronic acid content, total phenolic content (TPC) and antioxidant performance. A great influence of pH on the CBS extraction was observed, since alkaline conditions resulted in higher extraction yields and antioxidant capacity. Optimal MAE conditions were determined as 5 min, pH 12, 97 degrees C and S/L 0.04 g/mL showing better outcome than conventional solvent extraction. Antioxidant performance was evaluated by using colorimetric methods (FRAP, ABTS) while structural (FTIR), physico-chemical and functional properties of the MAE extracts were also determined. MAE extracts obtained at pH 12 were rich in proteins (580.0 mg BSA/g), polysaccharides (370.4 mg Glu/g) and polyphenols (35.9 mg GAE/g), showing important antioxidant performance (35.5 mg TE/g). It can be concluded that MAE is an efficient technique for the release of bioactive molecules from CBS with antioxidant performance and potential applications in the food industry.