(R,S)-Hydroxypropyl-modified β-cyclodextrin (RSP-CD) is a well-known chiral stationary phase. In this work, hydrophilic interaction liquid chromatographic (HILIC) selectivities of RSP-CD was demonstrated. Further, an evaluation of chromatographic performances of fully porous particles (FPPs)- and superficially porous particles (SPPs)-based RSP-CD stationary phases was performed. The RSP-CD-bonded SPP-based stationary phase showed faster and more efficient HILIC separations compared to the FPP-based stationary phases. In addition, the SPP-based RSP-CD stationary phase showed excellent selectivities for many classes of small polar molecules. Since the SPP-based stationary phase is allowed for separations performed at high flow rates without significant loss of efficiency, ultrafast separations (analysis times under 1 min) also was accomplished utilizing SPP-based RSP-CD stationary phase.