Yunnan Congou black tea (YCBT) is a typical black tea in China, and is rich in theaflavins (TFs), thearubigins (TRs), and theabrownins (TBs). However, the influence of the fermentation temperature and time on the liquor and appearance color and the correlation between the tea pigments and its color attributes remain unclear. We investigated the effects of the fermentation temperature and time on the color attributes and tea pigments of YCBT. A low fermentation temperature was beneficial to maintain a bright orange-red liquor color and promote the accumulation of TFs and TRs. In contrast, a high temperature gave the liquor a glossy appearance and was beneficial for the formation of TBs. A correlation analysis showed that the 10TFRB index best represented the contribution of tea pigments to the quality of black tea. Moreover, TRs and TBs content prediction models were established based on the liquor L and H values, where the former value can be used as an important index to judge the fermentation process. This study will further enrich the theory of black tea processing chemistry and provide technical support for the precise and directional production of black tea.