A novel supramolecular AIE (aggregationinduced 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 Fe 3+ , Hg 2+ , Ag + , F − , and Br − by the competition between "exo-wall" π−π interactions and cation−π interactions. The LODs (limits of lowest detection) of these AIE gels for Fe 3+ , Hg 2+ , Ag + , F − , and Br − are in the range of 7.3 × 10 −10 −9.5 × 10 −9 M, indicating high sensitivity. More importantly, the xerogel of PMDP-G could adsorb and separate Fe 3+ , Hg 2+ , and Ag + from aqueous solution with nice adsorption property, and the adsorption rates are in the range of 90.12−99.95%. Meanwhile, supramolecular AIE gel PMDP-G could be used as a smart fluorescent display material.