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Photocurable 3D printing of polyphenol‐based gels has been limited by the catechol groups, which can scavenge free radicals generated by photoinitiators during photopolymerization. Herein, a 3D‐printed gel composed of poly‐acrylamide (PAM) and tannic acid (TA) is presented, fabricated by using glycerol as shielding of TA and a commercial digital light processing printer. The printed gels are based on a polymeric network interpenetrated by TA‐glycerol, enabling the printed objects with various favorable properties, such as improved toughness, anti‐dehydration, antioxidant and antibacterial properties, etc. The proposed strategy enables photocurable 3D printing of polyphenol‐based gels with complex architecture, paving the way for future applications in various fields, ranging from soft wearable devices to tissue engineering.

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