The effect of mold rotation on the transport process and resultant macrosegregation pattern during solidification of an Al-Cu alloy contained in a vertical axisymmetric annular mold cooled from the inner wall is numerically investigated. The mold initially at rest starts to rotate at a prescribed angular velocity simultaneously with the beginning of cooling. Computed results for a representative case show that the mold rotation essentially suppresses the development of both thermal and solutal convections in the melt, creating distinct characteristics such as the liquidus front, flow pattern and temperature distribution from those for the stationary mold. Thermal convection which develops at the early stages of cooling is soon extinguished by the rotating flow induced during spin-up, and thus does not effectively remove the initial superheat from the melt. On the other hand, solutal convection, though it weakens considerably and is confined within the mushy zone, still predominates over the solute redistribution process. With increasing the angular velocity, the solute transport in the axial direction is enhanced, whereas that in the radial direction is reduced. The final macrosegregation formed in the mold rotating at moderate angular velocities appears to be favorable in comparison with the stationary casting, in that not only relatively homogenized composition is achieved, but also a severely positive-segregated channel is restrained.