A novel click oligo(ethylene glycol) (Click OEG) stationary phase was proposed for constructing two-dimensional reversed-phase/reversed-phase liquid chromatography system (2D-RP/RPLC) combined with C18. The new stationary phase was prepared by immobilization of oligo(ethylene glycol) on silica support via click chemistry. And the resulting material was characterized by FT-IR, solid state CP/MAS 13C NMR and elemental analysis. The investigation on orthogonality between Click OEG and C18 was performed by geometric approach with a set of test solutes. The orthogonality reached 68.94%, which is much higher than other combinations. An offline 2DLC system consisted of Click OEG and C18 was constructed and applied to the analysis of a kind of traditional Chinese medicine Lignum Dalbergiae Odoriferae. Excellent separation results validated the high orthogonality between the Click OEG and C18 in the practical separation of complex samples.