Abstract The construction of stimuli‐responsive materials by using naturally occurring molecules as building blocks has received increasing attention owing to their bioavailability, biocompatibility, and biodegradability. Herein, a symmetrical azobenzene‐functionalized natural glycyrrhizic acid (trans‐GAG) was synthesized and could form stable supramolecular gels in DMSO/H2O and MeOH/H2O. Owing to trans–cis isomerization, this gel exhibited typical light‐responsive behavior that led to a reversible gel–sol transition accompanied by a variation in morphology and rheology. Additionally, this trans‐GAG gel displayed a distinct injectable self‐healing property and outstanding biocompatibility. This work provides a simple yet rational strategy to fabricate stimuli‐responsive materials from naturally occurring, eco‐friendly molecules.