The extraction of pesticides from aqueous solutions using new ionic liquids (ILs) derived from glycine betaine as extractants was investigated. These ILs incorporate cationic esters of trimethyl(2-alkoxy-2-oxoethyl) ammonium (GBOCn+) associated with inorganic ClO4− or BF4− anions. First, batch extraction experiments were performed by using the liquid–liquid biphasic system IL/ethyl acetate/water (1:1:1; v/v) for four commonly used pesticides: 4-chlorophenoxyacetic acid (4-CPA), 2,4-dichlorophenoxyacetic acid (2,4-D), 2-[(4-methyl-5-oxo-3-propoxy-1,2,4-triazolin-1-yl)carbamidosulfonyl]benzoic acid methyl ester sodium salt (propoxycarbazone) and 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methoxymethyl nicotinic acid (imazamox). Then, the liquid–liquid extraction unit operation was intensified by transposing the system into a Centrifugal Partition Extraction (CPE) device, using ethyl acetate/n-butanol/water (1:4:5; v/v) as biphasic solvent system and potassium iodide, sodium iodide or sodium perchlorate as potential displacers. The use of a lab-scale CPE column with a capacity of 300 mL allowed the intensification of the extraction procedure. The extraction and back-extraction of individual or mixture of pesticides were studied, with a particular focus on the potential separation of individual pesticides and on the recyclability of the CPE method. In optimal CPE conditions, a quantitative extraction for three of the four pesticides was obtained, with recovery percentages of 95.6%, 98.7%, 99.0%, and 100.0% for imazamox, propoxycarbazone, 2,4-D, and 4-CPA, respectively. After the back-extraction step, separated pesticides were recovered in fresh aqueous mobile phase. The recyclability studies showed that the extraction/back-extraction process can be performed at least four times while maintaining a quantitative extraction.