During directional solidification of Cu–Ge peritectic alloys, a two-phase separated structure has been observed. With proper growth conditions, the peritectic ζ-Cu5Ge and primary α-Cu phases completely separate and form cylindrical layered structures. It is found that the formation of the separated structure is closely related to double diffusive convection and growth conditions. In the two-phase separated structure, a large trijunction region of peritectic reaction forms around the cylindrical α-Cu phase. During peritectic reaction, the morphological instabilities of ζ-Cu5Ge occur under high pulling velocities and are explained by the constitutional undercooling criterion. A new coupling growth between the ζ-Cu5Ge-phase and the groove of α-Cu phase near the trijunction is observed. Different from peritectic coupling growth, the diffusion coupling is established below the peritectic temperature. This two-phase separated growth process creates new opportunities for the fabrication of functionally layered materials.