A new strategy using non-porous silica (NPS) spheres as the support and covalent organic frameworks (COFs) as the porous functional shell for liquid chromatography was developed to ensure the independent effect of the COFs on the separation. As a proof of concept, NPS@TPB-DMTP was prepared for liquid chromatographic analysis using 1,3,5-tris(4-aminophenyl)benzene (TPB) and 2,5-dimethoxy-1,4-benzenedicarboxaldehyde (DMTP) as monomers by in situ polymerisation on the surface of NPS. It is a new way of developing COF-based stationary phases, which will be helpful in understanding what effect the COFs will have on separation.