In this paper, the selectivity of poly(4-methyl-5-vinylthiazole) stationary phase (PMV CA phase) is comprehensively studied in reversed-phase liquid chromatography (RPLC) mode with methanol-water system. The selectivity difference between PMV CA phase and three commonly used RPLC stationary phases (C18, C8 and Phenyl phase) is shown. Four typical species of standards (alkylbenzens, chlorobenzenes, nitrobenzenes and PAHs) are selected for the selectivity study. It is shown that the PMV CA phase has some special selectivities: 1) It has different selectivity from C18 and C8 phase because the PMV CA phase may form diploe interaction, pi-electron interaction and hydrogen bonding interaction (with the nitrogen atom and oxygen atom on the phase) with solutes owing to its polar aromatic thiazole ring and polar ester bond etc. on the phase; 2) It has similar property as phenyl phase because both of them can form pi-electron interaction with solutes. But owing to its polar thiazole ring and other polar group on the phase, which may form dipole interaction and hydrogen bonding interaction with solutes, there are still some differences between these two phases.