The limitations of conventional gas chromatography–mass spectrometry (GC–MS) analyses for alkyl- and aryl-tin compounds are discussed, particularly the excessive fragmentation from electron impact (EI) ionization. Negative EI methods exhibit low ionization capabilities and are restricted to compounds with an electronegative centre, and are thus not suitable for general routine analysis. Liquid chromatography–MS (LC–MS) interfaces offer potential advantages in terms of reduced sample work-up since no derivatization is required. Electrospray techniques give reproducible mass spectra for each compound studied under fixed instrumental parameters. Changes in the cone/repeller voltages can radically alter the observed mass spectra. High-mass species were observed for each compound studied and tentative structures for these species are proposed.