The structural evolution and segregation in a dual alloy made by electroslag remelting (ESR) was investigated by various analytical techniques. The results show that the macrostructure of the ingot consists of two crystallization structures: one is a quite narrow, fine, equiaxed grain region at the edge and the other is a columnar grain region, which plays a leading role. The typical columnar structure shows no discontinuity between the CrMoV, NiCrMoV, and transition zones. The average secondary arm-spacing is coarsened from 35.3 to 49.2 μm and 61.5 μm from the bottom to the top of the ingot. The distinctive features of the structure are attributed to the different cooling conditions during the ESR process. The Ni, Cr, and C contents markedly increase in the transition zone (TZ) and show a slight increase from the bottom to the top and from the surface to the center of the ESR ingot due to the partition ratios, gravity segregation, the thermal buoyancy flow, the solutal buoyancy flow, and the inward Lorentz force. Less dendrite segregation exists in the CrMoV zone and the transition zone due to a stronger cooling rate (11.1 and 4.5 °C/s) and lower Cr and C contents. The precipitation of carbides was observed in the ingot due to a lower solid solubility of the carbon element in the α phase.