Display omitted •Quantitative analytical method of nine monosaccharides.•Change of monosaccharides during processing of KBT.•Theaflavins inhibit the caramelization of D-glucose.•Theaflavins-glucose adducts were identified. Monosaccharides of Keemun black tea were quantitatively determined by high performance liquid chromatography coupled with 3-methyl-1-phenyl-2-pyrazolin-5-one (PMP) pre-column derivatization. The methodology of developed analytical method was established with good linearity, recovery, repeatability and precision. The quantitative results showed that D-mannose, D-glucuronic acid, D-glucose, D-galactose and L-arabinose were detected in Keemun black tea samples. D-glucose was the predominant monosaccharide in black tea, and its concentration was continuously increased from fresh tea leaves to fermentation, but after drying its concentration was significantly decreased. Meanwhile, theaflavins’ concentrations were obviously decreased after drying. When theaflavins were heated with D-glucose, the loss of theaflavins was increased. Correspondingly, theaflavins also prevented the caramelization of D-glucose and restored the loss of D-glucose during heating. Through the liquid chromatography/electrospray tandem mass spectrometry some theaflavins glucose adducts were identified.