Pyrene (Py) excimer, through its unique fluorescence quenching, exhibits high sensitivity and high selectivity in detecting specific electron-deficient molecules, providing a potential platform for sensing technology, optical switch and probing hydrophobicity of molecular environment. In solution state, its quenching mechanism has been well studied. However, there remain many unknown properties regarding the quenching mechanism of the solid-state Py excimer. In this paper, the effects of a series of tetraalkylammonium salts (with a variety of chain lengths and anions) on Py excimer quenching are investigated in order to identify the controlling parameters of the fluorescence quenching in the binary system. Several experimental approaches including steady-state fluorescence spectroscopy, UV absorption, (13)C-nuclear magnetic resonance (NMR) spectra, X-ray diffraction, scanning electron microscopy, and time-dependent fluorescence decay are employed in order to seek for the fundamental understanding of the quenching mechanism. The result indicates a unique quenching effect of tetrabutylammonium cation on the pyrene excimer, and which is not observed in the other cations with different chain lengths (the same associated hexafluorophosphate anions). Meanwhile, hexafluorophosphate anion (in presence of tetrabutylammonium) is able to effectively retain Py excimer fluorescence when the system is prepared by evaporating solvent at high temperature. It is also confirmed that dynamic quenching is involved in the process. Hydrophobic environment around Py molecules shows strong correlation with the formation of Py excimer. The knowledge obtained in this study provides the insights to how the interaction between salt and Py molecule affects the excimer fluorescence.