The antioxidant, whitening, antibacterial activities, cytotoxicity and skin permeability effects of volatile oil of Salvia miltiorrhiza, dandelion extract and their complexes were tested, and the synergistic effects of S. miltiorrhiza volatile oil and dandelion extract were investigated. The results showed that the antioxidant activity of the complexes was stronger than that of the two alone, and slightly higher than that of the positive control VC. The results of enzyme kinetics showed that the inhibitory effect of volatile oil on tyrosinase activity was stronger than that of arbutin, the positive control. The inhibitory type of volatile oil on tyrosinase was competitive, and the inhibition constant KI was 0.0049 mg/L. There was no antagonistic effect between volatile oil and dandelion on tyrosinase activity. The inhibitory effect of the complexes on Staphylococcus aureus were better than that of the single component, which was comparable to the positive control, streptomycin sulfate. The extract had no cytotoxicity when the concentration reached 100 mg/L. After complexing the S. miltiorrhiza volatile oil and dandelion extract, the cumulative permeability of dandelion extract was greater than when acting alone, and the volatile oil of S. miltiorrhiza promoted the transdermal absorption of dandelion extract. The results showed that the complex of S. miltiorrhiza volatile oil and dandelion extract had synergistic antioxidant and antibacterial effects, no obvious cytotoxicity, better skin permeability, and could be used as a natural active substance in food, cosmetics and other fields.