Impact ionization in novel Ge/Al x Ga 1−x As (0≤ x ≤ 0.8) multilayer structures is investigated using numerical simulation. The simulated effective electron (ᾱ) and hole (β) ionization coefficients reveal that a largeβ/ᾱ ratio of up to 8 can be obtained in a 25-period Ge (50 nm)/Al 0.8 Ga 0.2 As (50 nm) multilayer structure, much larger than that in the Ge and Al x Ga 1−x As homojunctions, attributed by the reduction inᾱ. The substantial difference in phonon scattering cross-sections in the Al x Ga 1−x As barrier and the Ge well played an important role in determining theβ/ᾱ ratio in these structures. Breakdown voltage analysis indicates that hot carriers' drift in the Al x Ga 1−x As barriers and Ge wells sampled the transport properties of both materials, despite the electron and hole ionizations are dominated by that of Ge within the electric field range studied.