Centrifugal partition chromatography (CPC) is a support-free liquid–liquid separation process that depends for efficiency on the behavior of the two liquid phases. Hydrodynamics of phases was studied according to flow rate and centrifugal acceleration, using a transparent column and a stroboscopic video system. For the heptane-methanol two-phase system, three main flow regimes—stuck film, oscillating sheet, and atomization—are observed, highlighting the coriolis acceleration effect as well as the influence of the column shape. Mass transport in the CPC column is modeled by a plug flow with axial dispersion and mass transfer with a stagnant volume. Model parameters (residence time, Péclet number, partition ratio, and mass-transfer coefficient) are fitted on solute residence-time distribution. Off-column dispersion is an important source of peak broadening in CPC, whereas its irregular geometry provides a plug flow for mobile phase. Importance of flow pattern on mass transfer is demonstrated. CPC interest for preparative applications is confirmed.