Studies of clusters in condensed phase at atmospheric pressure are very important for understanding the properties and structures of liquids. Liquid-ionization (LPI) mass spectrometry is useful to study hydrogen-bonded clusters at the liquid surface and in a gas phase. An improved ion source connected to a tandem mass spectrometer provides detailed information about clusters. Mass spectra of pure ethanol (99.5%) observed by the first mass analyzer (Q1) showed neat ethanol cluster ions (C₂H₅OH)_mH⁺ with m up to 10 and hydrate ions (C₂H₅OH)_m(H₂O)_nH⁺ with m larger than 7 and n=1, such as those with m-n=8-1 and 9-1. When the flow rate of ethanol (liquid) was increased, large ethanol cluster ions with m larger than 25 were observed by the second mass analyzer (Q3). It is interesting to note that neat ethanol cluster ions are more abundant than corresponding (with the same m) hydrate ions (n=1), and major hydrate ions contain only one molecule of water. Results indicate that ion–molecule reactions occur between Q1 and Q3, because such mass spectra have never been observed by Q1. Various results indicate that neat ethanol clusters exist at the liquid surface and are ionized to give cluster ions.