An important problem associated with the development of continuous process for the extraction and separation of Co(II) and Ni(II) is the decrease in the pH of the aqueous phase after its equilibration with organic solvent containing cationic extractants such as Cyanex 272, LIX 860, etc. An improvement in the solvent extraction and separation of Co(II) and Ni(II) from neutral chloride solutions is obtained using ionic liquid extractant tertiary alkyl (C16–C22) primary ammonium bis 2,4,4-(trimethylpentyl) phosphinate (HJMT–Cy272) generated by reacting primary amine, Primene®JMT (JMT) and bis(2,4,4-trimethylpentyl)phosphinic acid, Cyanex 272 (Cy272) in the organic phase. The presence of JMT allows to control the pH of the equilibrated aqueous phase during the extractions of Co(II) and Ni(II). This has facilitated the application of continuous counter current liquid–liquid extraction in the given metal extraction system without applying any in-between acid neutralization process. The liquid–liquid extractions were carried out under different experimental conditions such as concentration of JMT and Cy272 in the organic phase, and concentration of metal ions in the aqueous phase. The optimized composition of the organic phase to obtain better recovery and separation of Co(II) and Ni(II) is 10% Cy272 + 10% JMT in D100. The equal percentage of Cy272 and JMT in the organic phase gave minimum change in the pH of the aqueous phase before and after its equilibration. The McCabe-Thiele plot suggested three theoretical stages of counter current operation for obtaining greater than 99% extraction of Co(II) from its 1 g/L solution. For two metal system, four stage counter current extraction was carried out using bench scale mixer–settler equipment which gave > 99% extraction of Co(II) along with 11% of Ni in the organic phase whereas about 89% of Ni(II) with about 0.3% of Co(II) remained in the aqueous phase. The loaded organic phase was treated with 0.02 M EDTA to strip metal ions and the same was used successfully for the second run of the extraction and stripping process.