Tea wine is a beverage that combines the flavors of tea and wine with a variety of health benefits and has thus attracted widespread attention. However, few systematic studies have focused on dark tea wine, particularly on the dynamic changes in dark tea wine aroma. A sensory evaluation was conducted based on process optimization, and headspace solid-phase microextraction combined with gas chromatography-mass spectrometry was used to analyze the volatile components of dark tea wine. The results showed that dark tea wine gradually showed the sensory characteristics of wine as fermentation proceeded, presenting a strong and lasting herbal, spicy and sweet flavor. During fermentation, both the type and content of volatile components increased, especially higher alcohols and esters, which impart green, fruity, and sweet aromas. Aroma formation in dark tea wine occurs mainly during the late stages of fermentation. The monoterpenoid biosynthesis, fatty acid biosynthesis, lipoic acid metabolism, and phenylalanine metabolism pathways play roles in the unique aroma of dark tea wine. These results provide a theoretical basis for studying the aroma formation mechanism of dark tea wine and quality control of fermented dark tea wine in the future.