Honey is known to promote alcohol metabolism effectively. However, the effects of its individual chemical components system on alcohol metabolism and their mechanisms of action have not yet been fully elucidated. We constructed polyphenols and ascorbic acid systems (PAAS) of six different floral kinds of honey by exogenous substances, to investigate their effects on alcohol metabolism in the liver. PAAS consists of 22 kinds of polyphenols (including arbutin and caffeic acid) and ascorbic acid. The results demonstrated that PAAS improved the activity of alcohol dehydrogenase (ADH) and the expression of adh1, but had no significant effect on acetaldehyde dehydrogenase (ALDH) and expression of adh2, which caused a decrease in blood ethanol concentration but no difference in acetaldehyde concentration. Correlation analysis illustrated that arbutin and trans-4-hydroxycinnamic acid in PAAS were important potential substances for promoting alcohol metabolism. In addition, PAAS could also reduce the deleterious effects of alcohol by modulating unsaturated fatty acid biosynthesis, purine metabolism, and other metabolic pathways in the liver. These findings revealed the mechanisms by which PAAS promoted hepatic alcohol metabolism as well as protected the liver and provided a theoretical basis for exploring the mechanisms in honey synergistically promote alcohol metabolism.