The presented study gives an integrated overview on the prospects of glow discharge (GD) methods in the chemical analysis of photovoltaic materials. With a focus on recent research and important photovoltaic (PV) materials, the GD coupled analytical methods, high resolution mass spectrometry (MS), time-of-flight-mass spectrometry (TOF-MS) and optical emission spectrometry (OES) are discussed. Each exemplary study carried out will point out the most suitable GD technique for the problem at hand, at the same time showing ways to increase analytical accuracy and to overcome typical instrumental restrictions. Challenging GD-MS analyses of thin and ultra thin films (down to 20 nm) as well as GD-MS and GD-OES studies of ready-to-use modules were carried out, showing the reader the application potential of GD methods in a PV development or production process. For the first time, novel cell concepts based on crystalline silicon on glass and silicon nanowires are analyzed by GD-OES, revealing precise chemical information on the devices. Copyright © 2012 John Wiley & Sons, Ltd.