This review is focused on planar chromatography hyphenated with mass-spectrometric detection for analysis of low-molecular-mass solutes. Various kinds of hyphenations are discussed with attention paid to the preparation of thin layer plates suited both for the mass-spectrometric detection of the resolved solutes direct from thin-layer plates and for indirect mass-spectrometric detection of the resolved solutes, performed by scraping, extracting, purifying, and concentrating the analyte from the thin-layer chromatography plate. Plates with monolithic layers are relatively new for thin-layer chromatography but they can successfully be combined with mass-spectrometric technique in a pursuit of comprehensive local sample composition information. Preparation of monolithic layers of different porosity and structure based on organic, inorganic, and composite materials is illustrated together with examples of successful separation and detection of low-molecular-mass solutes by means of matrix-assisted and surface-assisted laser desorption mass spectrometry.