<p>C18-modified bipyridinium-functionalized silica was prepared and further modified with tetras(4-sulfonatophenyl)styrene (TPE-SO₃H) via ion bonding. Thus, two novel stationary phases, including C18-modified bipyridinium stationary phase (Sil-DPC18) and TPE-SO₃H-functionalized C18-modified bipyridinium stationary phase (Sil-DPC18-TPES) were obtained. The stationary phases were characterized by elemental analysis and Fourier transform infrared spectroscopy (FT-IR). The reversed-phase chromatographic performance of Sil-DPC18 and Sil-DPC18-TPES were evaluated using the Tanaka test mixture, alkylbenzenes, and linear polycyclic aromatic hydrocarbons (PAHs). Compared to an in-house Sil-C18, Sil-DPC18-TPES and Sil-DPC18 exhibited stronger aromatic selectivity and shape selectivity, but weaker hydrophobicity and hydrophobic selectivity. Furthermore, Sil-DPC18-TPES demonstrated better hydrophobicity, hydrophobic selectivity, aromatic selectivity and shape selectivity compared to Sil-DPC18. The enhancement could be due to the introduction of TPE-SO₃H. In addition, Sil-DPC18-TPES and Sil-DPC18 exhibited good separation selectivity for PAHs, phenylesters, phenols, and phenylamines compared to Sil-C18.</p>