•Immobilization of Ni2+ ions at the inner surface of monodisperse spherical mesoporous SiO2 particles.•Monodisperse spherical mesoporous SiO2/Ni particles of 500±25nm diameter as metal affinity sorbents.•Diclofenac extraction by IMAC technique.•Addition of PFOS to IMAC eluents improves the recovery degree of diclofenac (up to 98%).•The obtained thermodynamics analysis data indicate the chemical nature of the DCF interaction with the surface of the sorbent. In this research, a novel IMAC sorbent with high specificity for chlorine-containing compounds was developed. Ni-functionalized monodisperse spherical mesoporous silica particles of 500±25nm diameter were synthesized and their metal affinity properties were studied with the use of diclofenac as the model substance. The particles were aggregatively stable in the pH range of 3–12. The sorbent demonstrated a high adsorption capacity (0.60±0.06μg of DCF per 1mg of the sorbent) and high adsorption/desorption rate (20 and 5min was enough for the sorbent saturation and desorption of DCF, correspondingly). A mixture of eluents with addition of PFOS providing the almost complete recovery (98%) of diclofenac was first proposed. The monodispersity and the high sedimentation and aggregative stability of the particles provide the formation of a stable hydrosol even under ultrasound treatment which makes the mSiO2/Ni particles suitable for batch chromatography.