Carbon dots (CDs) are new carbon nanomaterials, among which those prepared from biomass are popular due to their excellent optical properties and environmental friendliness. As representative natural phenolic compounds, tea polyphenols are ideal precursors with fluorescent aromatic rings and phenolic hydroxyl structures. Usually, polyphenolic precursors can only be used to produce blue or green fluorescent CDs, and fluorescence in long wavelength domains, such as orange or red, cannot be achieved. Herein, the high reactivity of the phenolic hydroxyl groups in tea polyphenols with o -phthalaldehyde was exploited to modulate the pH during the carbonation process, which led to redshifts of the fluorescence wavelengths. Different pH values during the reaction caused the precursors to take different reaction paths and form fluorescent groups exhibiting different conjugated structures, resulting in carbon dots providing different fluorescent colors. Finally, by utilizing the in situ hydrolysis of ethyl orthosilicate, the tea polyphenol-based carbon dots were embedded into a silica matrix, inducing phosphorescence of the carbon dots. This study provides a new approach for green preparation and application of natural polyphenolic CDs.