The matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF) and micellar electrokinetic chromatography (MEKC) methods were used to identify and quantify five tannins, (+)-catechin, (−)-epigallocatechin, (−)-epigallocatechin gallate, (−)-epicatechin gallate and (−)-epicatechin, from aqueous, ethanolic and acetonic extracts of Calendula officinalis, Hy-pericum, perforatum, Galium verum and Origanum vulgare. The MALDI-TOF technique was used for screening tannins monomers and oligomers in plant extracts. The sandwich method and matrix 2,5-dihydroxybenzoic acid with a concentration of 10 mg mL−1 in acetonitrile/ultrapure water/trifluoroacetic acid (20: 80: 0.1, vol.) were used. The electrophoretic method developed for the separation and quantification of 5 catechins in 15 min exhibited good efficiency and precision, low limits of detection (0.0032–0.0153 μ.g mL-1) and quantification (0.0096–0.0466 μ.g mL−1). The correlation coefficients (R2) exceeded 0.9986 and the recovery values ranged between 94.25 % and 102.50 %. The present work provides new information on some of the less studied compounds present in plants frequently used in traditional medicine.