A series of salts based on ethyl ester glycine-betaine derivatives, viz tri(n-pentyl)[2-ethoxy-2-oxoethyl]ammonium bromide, have been synthesized. These cations generate hydrophobic ionic liquids (ILs) with bis(trifluoromethylsulfonyl)imide (Tf2N−) or dicyanamide (Dca−) anions. These new analogues of glycine-betaine-based ionic liquids (AGB-ILs) were characterized using spectroscopic methods (IR, 1H, and 13C NMR) and elemental analysis. These AGB-ILs were used for the selective separation of Ni(II) and Co(II) in saline media using pure ILs phase or ILs diluted in organic solvent. Interestingly, extraction of Co(II) and Ni(II) in Dca-based AGB-ILs can be enhanced using salts with chaotropic anions such as NaNO3 (E > 90% for Co(II) and E = 85% for Ni(II)). Tf2N−-based ionic liquids do not extract Ni(II) or Co(II) even in NaCl 4M. Dca−-based ILs lead to a quasi-quantitative extraction of Co(II), while extraction of Ni(II) is limited to a few percent (17%) leading to separation factors higher than 100, ensuring a good separation of both metals. Cobalt could be back-extracted from the ionic liquid phase with water or with an aqueous solution of Na2SO4, which limits the release of the AGB cation in aqueous media, thus preserving its integrity. Results obtained by AGB-ILs diluted in organic solvent were comparable to those obtained with the pure AGB-ILs phase, indicating that this strategy can be deployed on systems working continuously out of equilibrium since the extraction mechanisms involve fast equilibria.