A neutral naphthyl methacrylate-based monolith (NMM) was introduced for RP-CEC of various aromatic compounds via hydrophobic and it interactions It was characterized over a wide range of elution conditions to gain Insight into its RP retention mechanism toward the various solute probes under investigation. First, the NMM column exhibited cathodal EOF at various mobile phase compositions and pH suggesting that although the NMM column is void of fixed charges, it acquires a negative zeta potential. It is believed that the negative zeta potential is imparted by the adsorption of mobile phase ions to the NMM surface. The NMM column exhibited pi-pi interactions in addition to hydrophobic interactions due to the aromatic and nonpolar nature of its naphthyl ligands In all cases, the retention of the various aromatic test solutes including PAHs, benzene derivatives, toluene derivatives, anilines and toluidine, tolunitrile and nitrotoluene positional isomers on the NMM column were compared to their retention on an octadecyl acrylate-based monolithic column. Not only were the values of the retention factors of the various solutes on the NMM column higher than those obtained on the octadecyl acrylate-based monolithic column under otherwise the same CEC conditions, but the elution orders were also different on both columns with a superior and unique selectivity exhibited by the NMM column.