A novel supramolecular AIE (aggregation-induced emission) gel (PMDP-G) based on pillar[5]arene which could ultrasensitively detect and separate multianalytes was efficiently constructed. First, a novel supramolecular gelator, PM (host), and a functionalized pillar[5]arene, DP (guest), were successfully designed and synthesized. Then, host PM and guest DP could construct a stable supramolecular AIE gel, PMDP-G, via “exo-wall” π–π interactions and host–guest interactions in cyclohexanol solution. Interestingly, PMDP-G shows bright blue-white AIE and the fluorescence quantum yield is about 60%. Moreover, PMDP-G could carry out ultrasensitive detection and separation of multianalytes such as Fe3+, Hg2+, Ag+, F–, and Br– by the competition bet...