Maintaining the vibrant color of fruit is a longstanding challenge in fruit and vegetable preservation. Chitosan and selenium, known for their protective and antioxidant properties, have been applied to preserve these produce. This study aimed to investigate the influence of selenium–chitosan treatment (comprising 25 mg L−1 selenium and 1.0% chitosan) on the color of “Red Globe” grapes and to analyze the relative expression of genes associated with anthocyanin synthesis enzymes (VvCHS, VvCHI, VvF3H, VvF3′H, VvF3′5′H, VvDFR, VvLDOX, VvUFGT, VvOMT, Vv5GT, and VvGST) using RT-qPCR. Our goal was to uncover the regulatory mechanisms governing grape color. Comparing various treatments, we observed that selenium–chitosan treatment had a significant effect in reducing decay, maintaining the soluble solids content of grape flesh, and preserving the vivid color of grape. This research indicated that selenium–chitosan treatment slowed down browning and prevented the reduction in total phenolic, flavonoids, and anthocyanin in the grape. Moreover, gene expression analysis revealed that selenium–chitosan treatment increased the expression of VvCHS, VvF3H, VvF’3′H, VvLDOX, and Vv5GT, while also stabilized the expression of VvCHI, VvF3′H, and VvDFR in grape skins. These findings shed light on the potential mechanism by which selenium–chitosan impacts grape color. This study established a theoretical foundation for investigating the molecular mechanisms behind selenium–chitosan’s ability to slow down grape browning and provides a novel approach to enhancing fruit and vegetable preservation techniques.