In the field of cosmetics, epigallocatechin gallate (EGCG) is highly valued for its multiple effects such as delaying photoaging, whitening, anti-allergy, acne removal, astringency, and moisturizing. However, due to the active chemical properties of EGCG, there are challenges in terms of stability and transdermal absorption, which limits its widespread application in cosmetics. Therefore, we utilized supramolecular modification technology to form supramolecular carboxymethyl chitosan-EGCG-trehalose (CC-EGCG) by combining EGCG with carboxymethyl chitosan and trehalose, enhancing its stability. Then, we encapsulated the supramolecular CC-EGCG with hydroxypropyl cyclodextrin to obtain a dual supramolecular CC-EGCG, which not only further enhanced the stability of the raw material and reduced its irritation to the skin but also improved skin permeability (compared with single EGCG, the dual supramolecular CC-EGCG increased by 3.51 times). The bioavailability of EGCG was significantly improved, making it play a better role in antioxidant, whitening, soothing, and oil control acne removal.