The effect of cooling rate and iron content on the solidification structures of copper-iron alloys had been investigated in this paper. The results show that the morphology of as-cast structure is mainly determined by iron content and the grain size is affected by both the iron content and cooling rate. The as-cast structure is obviously refined and its morphology changes gradually from columnar grains to equiaxed ones with the increase in iron content. When iron content is greater than 3% (in mass%) the as-cast structure is composed wholly of equiaxed grains. With the increase in cooling rate the as-cast structure is gradually refined and primary γ-Fe phase is gradually scattered uniformly throughout the matrix.