Recently, core-shell-type stationary phases have been widely employed in reversed-phase liquid chromatography (RPLC) because of its good separation performance.  However, the reports for the RPLC separation on a core-shell stationary phase at subambient temperatures are somewhat limited.  In this study, we investigated the separation behavior of polycyclic aromatic compounds on a core-shell-type octadecylsilica (ODS) phase at subambient column temperatures in RPLC.  As expected, the plate height of the core-shell ODS phase was significantly smaller than that on conventional ODS phases.  In addition, the plate height on the core-shell ODS phase was relatively stable when changing the column temperature.  An improved molecular shape selectivity of core-shell phase at subambient column temperatures was also confirmed.  Although an improvement in molecular shape selectivity is commonly observed on conventional ODS phases at subambient column temperatures, it was somewhat difficult to perfectly separate the critical pair, benz[a]anthracene and chrysene, having closely related structures.  On the other hand, an enhanced molecular shape recognition capability of the core-shell-type phase allowed almost baseline separation of the solute pair at a column temperature around -15℃.  Similar improved molecular shape recognition capabilities for terphenyl isomers were also confirmed on the core-shell-type phase.