In order to identify and analyze the characteristics of the volatile and key aroma components of Congou black tea varieties, automatic thermal desorption-gas chromatography-mass spectrometry (ATD-GC-MS) was used in combination with relative odor activity values (ROAVs). The results revealed that 96 types of volatile components were identified from five Congou black tea varieties, including 18 types of common volatile substances. Examples of these were alcohols, aldehydes, ketones, alkenes, esters, acids, and alkanes, amongst other components. The five Congou black tea varieties mainly presented floral, fruity, and sweet aromas, with the six of main aroma components being decanal, linalool, benzyl alcohol, geraniol, hexanal, and isovaleraldehyde. The volatile components and their relative contents across the five Congou black tea varieties were significantly different. Among them, Golden Peony had a higher content of esters and ketones, whereas Golden Guanyin had a higher content of alcohols and aldehydes. Purple Rose had a higher content of alcohols and ketones, and the Meizhan variety was rich in alcohols. Fuyun 6 also had a higher content of alcohols and ketones. In addition, in combination with the ROAV values, this study selected 7 to 15 aroma components which contributed remarkably to the aroma quality characteristics of the five Congou black tea varieties (ROAV≥1.00).