In the present work, detailed analysis on flow characteristics of a pair of immiscible liquids through horizontal pipeline is simulated by using ANSYS FLUENT 6.2. Moderately viscous oil and water (viscosity ratio = 107, density ratio = 0.89 and interfacial tension = 0.024 N/m) have been taken as system fluids for the study. Volume of Fluid (VOF) method has been employed by assuming unsteady flow, immiscible liquid pair, constant liquid properties, and co-axial flow. Meshing has been done using GAMBIT. Quadrilateral mesh type has been chosen to account for the surface tension effect more accurately. From the grid independent study, we have selected 47037 number of mesh elements for the entire geometry. Simulation successfully predicts slug, stratified wavy, stratified mixed and annular flow, except dispersion of oil in water, and dispersion of water in oil. Simulation results are validated with horizontal literature data and good conformity is observed. Subsequently, we have simulated the hydrodynamics (viz., velocity profile, area average pressure across a cross section and volume fraction profile along the radius) of stratified wavy and annular flow at different phase velocities. The simulation results show that in the annular flow, total pressure of the mixture decreases with increase in oil velocity due to the fact that pipe cross section is completely wetted with water. Simulated oil volume fraction shows maximum at the centre in core annular flow, whereas, in stratified flow, maximum value appears at upper side of the pipeline. These results are in accord with the actual flow configuration. Our findings could be useful in designing pipeline for transportation of crude oil.