A solid-phase absorbent obtained by the immobilization of Aliquat 336 chloride in poly(vinyl chloride) is reported to extract preferentially Co(II) from its 7M hydrochloric acid solutions containing Ni(II). Under the experimental conditions there was no extraction of Ni(II) which allowed the complete separation of these two ions. Co(II) was rapidly and quantitatively back-extracted with deionised water. A mechanism for the extraction of Co(II) is proposed based on the formation of the ion-pair A(+)[HCoCl(4)](-) where A(+) is the Aliquat 336 cation. Fe(III) and Cd(II), usually present in Co(II) and Ni(II) samples, were also extracted into the solid-phase absorbent though at a slower rate than Co(II) and they did not interfere with the separation of Co(II) from Ni(II). It was also demonstrated that this approach allowed the complete separation of Ni(II) from the other metal ions mentioned above.