Isatindigotindolosides, indoles containing a 1-S-beta-glucopyranosyl unit at position C2, show promising bioactivity. Here, we report a copper-catalyzed C2- or C3-thioglycosylation of indoles with N-(thioglycosides)succinimides to construct indole alkaloid glucosides. This reaction is widely tolerant of functional groups, as various indoles and thioglycosides are suitable. It also provides a reliable method for performing late-stage modifications of natural products, such as gramine and melatonin. Total syntheses of isatindigotindolosides I and II were successfully accomplished using the C2-thioglycosylation reaction as a key step.