In this study, we developed a novel cationic Bletilla striata polysaccharide (CBSP)/Carbopol ETD 2020 (CP) composite hydrogel matrix (CBSP-CP) for local drug delivery of traditional Chinese medicine formulations and compounds. This approach addresses the shortcomings of the existing commercial gel matrices in delivering complex components. We used molecular dynamics simulations to confirm the feasibility of crosslinking and compounding the polymer components. The structure of the composite was characterized using various traditional methods, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The composite polyelectrolyte hydrogel prepared through electrostatic interactions between CBSP and CP exhibited favorable rheological properties, excellent ion resistance stability, and good skin adaptability. Furthermore, the safety of the gel matrix was validated using cytotoxicity and skin irritation tests. In summary, the CBSP-CP gel matrix not only enhanced ion resistance compared to current commercial gel matrices but also expanded its applicability for the local delivery of complex components, such as traditional Chinese medicine formulations and compounds.