Barbatimão (Stryphnodendron adstringens) is a Brazilian medicinal plant known for its pharmacological properties, including healing activity related to its phenolic composition, which is chiefly given by tannins. In order to preserve its stability and bioactivity, barbatimão extracts can be incorporated into (bio-)polymeric matrixes, of which silk fibroin stands out due to its versatility and tunable properties. This work aimed to obtain barbatimão bark extract rich in phenolic compounds and evaluate its incorporation in fibroin hydrogels. From the extraction process, it was observed that the PG (propylene glycol) extract presented a higher global yield (X0) and phenolic compounds (TPC) than the ET (ethanol) extract. Furthermore, the antioxidant activity (ORAC and FRAP) was similar between both extracts. Regarding the hydrogels, morphological, chemical, thermal, and mechanical characterizations were performed to understand the influence of the barbatimão extract and the solvent on the fibroin hydrogel properties. As a result, the hydrogels containing the barbatimão PG extract (BT/PG hydrogels) showed the better physical–chemical and structural performance. Therefore, these hydrogels should be further investigated regarding their potential in medical and pharmaceutical applications, especially in wound healing.