Multifunctional stimuli-responsive supramolecular polymers have applications in the field of smart materials. Herein, a tri-pillar[S]arene-based multifunctional stimuli-responsive supramolecular polymer network gel (SPN-DTG) was successfully constructed. Interestingly, the SPN-DTG shows excellent conductivity and tunable blue aggregation-induced emission (ALE) properties. Meanwhile, a series of metal-ion-coordinated supramolecular polymer network gels (MSPNs) were successfully constructed by rationally introducing various metal ions into SPN-DTG. The xerogel powder of SPN-DTG shows excellent separation capacity for the removal of Fe3+, Hg2+, Cu2+, and Co2+ from water. More importantly, the Co2+-coordinated supramolecular polymer network gel MSPN-Co shows intriguing thermochromic properties. The color of MSPN-Co could be reversibly controlled between light yellow and dark green by controlling the system temperature. In addition, the Fe3+-, Hg2+-, Cu2+-coordinated supramolecular polymer network gel MSPNs (Mn+ = Fe3+, Hg2+, Cu2+) show high selectivity and quick fluorescence response for I- and H2PO4-. Therefore, the SPN-DTG has applications in multifunctional smart materials with conductivity, ALE, thermochromism, fluorescence detection, and separation properties.