Mesoporous silica spheres were functionalized with microporous metal-organic frameworks (MOFs), namely MIL-101(Fe)_NH₂ (Fe₃(O)(BDC_NH₂)₃(OH)(H₂O)₂, BDC = benzene-1,4–dicarboxylate) and UiO-67 (Zr₆O₄(OH)₄(BPDC)₆, BPDC = 4,4′-biphenyldicarboxylate) to produce core-shell particles for application as stationary phase in high performance liquid chromatography (HPLC) columns using a layer-by-layer method. The composites were studied for application as stationary phase in normal phase HPLC for separation of C₈-isomers, dichlorobenzene isomers, styrene and ethylbenzene. Both silica/MOF composites show the highest affinity towards the ortho substituted analytes, indicating that the selectivity is dominated by the polarity of the analytes. Moreover, the UiO-67@SiO₂ composite shows high separation efficiency in the separation of dimethyl phthalate and diethyl phthalate, since the number of theoretical plates per meter is very high (37570 m⁻¹).