In this study, a novel aggregation-induced emission supramolecular organic framework (AIE SOF) with ultrasensitive response, termed FSOF , was constructed using a tri-pillar5arene-based foldamer. Interestingly, benefiting from the noise signal shielding properties of FSOF as well as the competition between the cation π and π π interactions, the FSOF shows an ultrasensitive response for multi-analytes, such as Fe 3+ , Hg 2+ and Cr 3+ . The limits of detection (LODs) of the FSOF for Fe 3+ , Hg 2+ and Cr 3+ are in the range of 9.40 × 10 −10 -1.86 × 10 −9 . More importantly, the xerogel of FSOF exhibits porous mesh structures, which could effect high-efficiency separation above metal ions from their aqueous solution, with adsorption percentages in the range 92.39-99.99%. In addition, by introducing metal ions into the FSOF , a series of metal ions coordinated supramolecular organic frameworks ( MSOFs ) were successfully constructed. Moreover, MSOFs show selective fluorescence "turn on" ultrasensitive detection CN − (LOD = 2.12 × 10 −9 ) and H 2 PO 4 − (LOD = 1.78 × 10 −9 ). This is a novel approach to construct SOFs through a tri-pillar5arene-based foldamer, and also provides a new way to achieve ultrasensitive detection and high-efficiency separation. A novel aggregation-induced emission supramolecular organic framework (AIE SOF) constructed using tri-pillar5arene-based foldamer which could be used for the ultrasensitive detection of multi-analytes.