The fluid dynamic behavior of a drop during a freely rising process is investigated using the volume of fluid (VOF) method in conjunction with the continuum surface force (CSF) model. A two-dimensional computational fluid dynamic model is used to describe the mass and momentum transport. Measurements of the rise velocity and the aspect ratio for the toluene/water system without mass transfer for diameters ranging from 3–5 mm were obtained using a high-speed camera. The simulation results showed excellent agreement with the experimental data. The effects of the physical properties on the drop rising velocities, aspect ratios, and coalescence behavior of two coaxial drops are also simulated and analyzed. The simulation results show that the laws for the variation of the fluid dynamic behavior with the physical properties of a system provide important guidelines for the design and operation in a liquid–liquid column.