A new fermentation method for kiwi wine was explored by developing the well-known medicinal and edible plant Cyclocarya paliurus (C. paliurus) to create more value with undersized kiwifruits. In this study, the changes in bioactive substances during the C. paliurus–kiwi winemaking process were analyzed on the basis of response surface optimization results, and the antioxidant capacity, aromatic compounds, and sensory quality of the C. paliurus–kiwi composite wine with kiwi wine and two commercial kiwi wines were compared. The results showed that DPPH radical, OH− radical, and ABTS+ scavenging rates remained at over 60.0%, 90.0%, and 70.0% in C. paliurus–kiwi wine, respectively. The total flavonoid content (TFC) and total polyphenol content (TPC) of C. paliurus–kiwi wine were significantly higher than those of the other three kiwi wines. C. paliurus–kiwi wine received the highest score and detected 43 volatile compounds. Ethyl hexanoate, which showed stronger fruity and sweet aromas, was one of the main aroma components of C. paliurus–kiwi wine and different from commercial wines. This wine has a good flavor with a natural and quality feeling of C. paliurus–kiwifruit extract, low-cost processing, and great market potential.