A series of amphiphilic platinum(II) complexes with tridentate N-donor ligands has been synthesized and characterized. Different supramolecular architectures are constructed using the amphiphilic molecules as the building blocks through the formation of Pt...Pt and pi-pi stacking interactions in aqueous media. The aggregation-deaggregation-aggregation self-assembly behavior together with obvious spectroscopic changes could be fine: tuned by the addition of THE in aqueous media. More interestingly, one of the complexes is found to show fast response and high selectivity toward alcohol and water vapors with good reversibility, leading to drastic color and luminescence changes, and hence unique dual switching behavior, with the water molecules readily displaced by the alcohol vapor. Rapid writing and erasure have been realized via the control of a jet or a stream of alcohol vapor flow. In addition, it has been employed as active materials in the fabrication of small-molecule solution-processable resistive memory devices, exhibiting stable and promising binary memory performance with thrshold voltages of ca. 3.4 V, high ON/OFF ratios of up to 105 and long retention times of over 10(4) s. The vapochromic and vapoluminescent materials are demonstrated to have potential applications in chemosensing, logic gates, VOC monitoring, and memory functions.