In this study, 1,4-butanediol diglycidyl ether (BDDE) and aniline were grafted on the silicon sphere surface for preparing the polar-embedded phenyl dendritic multi-mode stationary phase (Sil-BD-AN). Results of Fourier transform infrared spectrometry (FT-IR), scanning electron microscope (SEM), elemental analysis (EA) and thermogravimetric analysis (TGA) confirmed the successful construction of the multi-mode stationary phase. The prepared column showed mixed separation mechanisms including hydrophilic interaction chromatography (HILIC) and reversed-phase liquid chromatography (RPLC) that realized the separation of different kinds of analytes including polycyclic aromatic hydrocarbons (PAHs), anilines, nucleic bases, nucleosides, alkylbenzenes and positional isomers. Moreover, effects of chromatographic conditions with retention time, such as injected volume, column temperature and acetonitrile content, were also examined. Furthermore, the application of the Sil- BD-AN column was proved by the accurate determination of p-phenylenediamine (PPD) content in the hair dye. The above results affirmed that the Sil-BD-AN column has the application potential for separating complicated samples under multiple modes.