Supramolecular assemblies with reversible boronate ester linkages are facilely prepared via self-assembly between cyclodextrin-centered glycoclusters and 4,4′-(1,2-diphenylethene-1,2-diyl)bis(1,4-phenylene)diboronic acid (TPEDB). Such sphere-like assemblies have shown a typical aggregation-induced emission (AIE) effect and could act as fluorescent probes for the sensitive detection of phenols in water.