Ambient ionization mass spectrometry is achieved in a simple manner by loading a sample solution onto a corner of a microscope cover glass positioned in front of the inlet to a mass spectrometer and applying a high voltage to the sample. The resulting stream of charged droplets is stable, has no contamination from the substrate platform, and can be used repeatedly. The utility of droplet spray for in situ analysis and real-time monitoring of chemical reactions was demonstrated by the bis(cyclopentadienyl)zirconium dichloride (zirconocene dichloride)/methylaluminoxane, Cp2ZrCl2/MAO, homogeneously catalyzed polymerization of ethylene in various solutions. Reaction times ranged from seconds to minutes, and catalytically active species and polymeric products of ethylene were acquired and identified by tandem mass spectrometry.