Multidimensional supramol. assembly (CB[6]-PA) based on cucurbit[6]uril (CB[6]) was constructed via the outer-surface interactions of CB[6] with a structure-directing agent of pamoic acid (H2PA).Most impressively, crystal CB[6]-PA exhibited satisfactory selectivity for the capture of Cd2+ and Hg2+ cations, and released Cd2+ and Hg2+ cations under acidic condition.This reversible process allows for capturing applications of Cd2+ and Hg2+ cations.Furthermore, crystalline CB[6]-PA-Cd demonstrated enhanced fluorescence properties compared with H2PA ligands.CB[6]-PA-Cd could be employed for the precise detection of methylmalonic acid (EA or MMA) as a biomarker of septicemia.The introduction of EA resulted in the fluorescence quenching of CB[6]-PA-Cd, the mechanism of sensing EA was clearly elucidated.A portable detection platform was designed to augment the efficiency of EA detection.To promote biol. applications, the exceptional probe capable of exactly detecting EA in serum samples had been substantiated.CB[6]-PA-Cd exhibited a negligible cytotoxicity, favorable cytocompatibility, and good hemocompatibility.Thus, these results will bring about new enlightenment for the fabrication of light-emitting materials and high-resolution bio-imaging probes based on cucurbit[n]urils.