Recently, a new Co-Al-W-based alloy with ordered L1₂ structure has been attracted much attention of researchers, these alloys have higher melting point than Ni-base superalloys with morphologically identical microstructure, but grain defect formation caused by thermosolutal convection has become an important problem for its application. Magnetic field is always applied to damp the convection which reduces the formation of defects. However, there are hitherto few papers to investigate the effect of magnetic field on grain defects during Co-Al-W-based alloy directional solidification. In this work, The effect of high magnetic field on the solidification structure and macrosegregation in directionally solidified Co-Al-W-based alloy was investigated. The results showed that the application of longitudinal magnetic field can induce convection and cause deformation of the solid-liquid interface shape, forming the macrosegregation and the stray grains in the mushy zone at the pulling rate of 5 μm/s. With the increase of pulling rate, the macrosegregation and the stray grains disappeared gradually at 2 T magnetic field. While the transverse magnetic field was applied, the macrosegregation became serious and the number of the stray grains increased. The macrosegregation further became more serious and the columnar-to-equiaxed transition was induced after adding the Ta element. The main reason of undercooling nucleation and columnar-to-equiaxed transition (CET) was the microsegregation induced by thermoelectric magnetic convention.