A cationic water-soluble dipicolylamine (DPA)-containing alkynylplatinum(II) terpyridine complex has been synthesized and employed as a dual-selective probe for the detection of cations and anions. The complex was shown to exhibit a strong binding affinity toward Zn2+, whereas the zinc-bound adduct was found to demonstrate the capability of recognizing pyrophosphate (PPi). As evidenced by molecular modeling and various spectroscopic and spectrometric studies, including HR-ESI mass spectrometry, NMR spectroscopy, PXRD measurements, and UV-vis absorption and emission spectroscopy, a PPi anion was found to be capable of bridging two zinc-bound complex molecules in a clip-shaped fashion, which was further oligomerized through intermolecular Pt center dot center dot center dot Pt and pi-pi stacking interactions to form nanofibers with a hexagonal columnar phase. This work provides important insights into not only the construction of aesthetically pleasing supramolecular architectures but also the multifunctional probes, which offer great promise to the fields of biosensing and chemical sensing.