•Exogenous sucrose promoted grape berry ripening.•Sugar metabolism in grape berry was altered by exogenous application of sucrose.•Hexokinase inhibitor had a similar function to sucrose in modifying berry composition.•Sucrose application promotes anthocyanin and proanthocyanidin repartitioning during grape ripening. Sugar and its metabolism play a critical role in fruit quality and determine the accumulation characteristics of secondary metabolites. In this study, the dynamic changes in anthocyanin and proanthocyanidin (PA) accumulation during exogenous sugar application were investigated throughout the grape ripening stage, and the underlying biosynthesis mechanism was monitored. Results showed that exogenous sucrose and N-acetyl-d-glucosamine (hexokinase inhibitor, HI) promoted grape berry ripening. Exogenous application of sucrose and HI significantly increased the levels of soluble sugars and anthocyanins, while significantly decreased the levels of acids and PAs in grape berries. Exogenous sucrose and HI activated the transcription of the VvSPS, VvAI and VvNI genes but inhibited the transcription of VvHXK gene to alter sugar metabolism. Notably, the accumulation of anthocyanin compounds, particularly peonidin derivatives, significantly increased in the sucrose- and HI-treated berries by upregulating the transcription of anthocyanin biosynthesis genes, including VvCHS2, VvF3′H, VvDFR, VvLDOX, and VvUFGT, whereas the accumulation of PA units, such as (‒)-epicatechin, (+)-gallocatechin, and (‒)-epigallocatechin, was repressed by downregulating the transcription of the VvLAR2 and VvANR genes, which boosted anthocyanin and PA reprogramming. These results provide preliminary information on how to modulate the biosynthesis and accumulation of anthocyanins and PAs in grape berries by the exogenous application of sucrose and thus, to modify berry composition.