Plants are subjects of interest due to the secondary metabolites in their extracts which are promising as new pharmaceuticals. Phytochemistry do not have united system of sample preparation or analysis still due to different structure of plant cells, wide broad range of chemical properties and concentrations of bioactive compounds. Such challenges can be addressed in a green chemistry manner using new approaches through smart materials in routine monitoring and researches. Liquid smart materials, such as ionic liquids (ILs) and deep eutectic solvents (DESs) are attractive due to flexible properties, lots of extraction approaches, recycle potential, and direct compatibility with powerful analytical methods. In this study DES-based microextraction procedure with pH-switching was developed. Four choline chloride DESs were suggested as selective extraction phases for polar compounds from acetonitrile extracts. Method was successfully tested on four plants (Iris sibirica L., Hypericum perforatum L., Scutellaria baicalensis G, Citrus reticulata B.). Developed procedure was optimized and validated for the choline chloride – urea (1:2 mol/mol) DES that demonstrated better results in extraction. LOD for rutin was found as 0.05 mg ml−1. For low-polar compound, imidazolium ionic liquid-based dispersive liquid-liquid microextraction procedure was developed. 1-hexyl-3-methylimidazolium salts have demonstrated desired selectivity. The main factors influencing the extraction efficiency have been identified and optimized by design of experiment on two model plants (Iris sibirica L. and Scutellaria baicalensis G.). Validation procedures were done for thymol. LOD for thymol was found as 0.021 mg ml−1. The methods were compared with each other and traditional methanol extraction. The selectivity of the smart materials supports each other, usage of such extraction phases provides same or better results as obtained with methanol.