Extraction is a thermal separation process which is used in various industries because it can be conducted at mild process conditions. The most commonly used solvents are volatile organic solvents, which often represent an environmental problem. In order to make the process environmentally friendly, many investigations are devoted to the development of new solvents. Studies have shown that environmentally acceptable deep eutectic solvents can be an adequate replacement for volatile organic solvents. Recently, the application of deep eutectic solvents for the extraction of valuable natural compounds from plant materials has been investigated. Piperine, an alkaloid with characteristic pungent taste, can be extracted from pepper. Due to its properties piperine is widely used in households, as well as in medicine. This paper explores new process of piperine extraction from nine different types of pepper with the use of deep eutectic solvents. Phytochemical analysis of peppers was made by means of spectroscopic and chromatographic methods. Differences between different types of pepper have been investigated. It was proven that green pepper contains the highest concentration of piperine. Principal component analysis was applied on the obtained results. Based on the preliminary results, related to the solubility and structure of a recrystallized of piperine, choline chloride - ethylene glycol (1: 2.5) was chosen as the best solvent for the extraction of piperine from pepper. The extraction was carried out in a batch extractor equipped with magnetic stirrer at various ratios of the pepper in the suspension. For the crystallization of piperine from extract phase, water was used as an antisolvent. The solvent is recovered by evaporation under vacuum. In that way its multiple use is enabled.