The combination of planar chromatography with desorption/ionization mass-spectrometry (MS) techniques provides chemists with unique tools for fast and simple separation of mixtures followed by the detection of analytes by the most powerful analytical method. Since its introduction in the early 1990s, thin-layer chromatography (TLC)/matrix-assisted mass spectrometry (MALDI) has been used for the analysis of a wide range of analytes, including natural and synthetic organic compounds. Nowadays, new desorption/ionization approaches have been developed and applied in conjunction with planar chromatography competing with MALDI. This review covers recent developments in the combination of TLC with various desorption/ionization MS methods which were made in recent several years. Copyright © 2021 Borisov, Kanateva and Zhilyaev.