The band offsets and charge storage characteristics of atomic layer deposited high-k HfO2/TiO2 multilayers with ten periods in p-Si/SiO2/(HfO2/TiO2)/Al2O3 structure have been investigated. The thickness of high-k HfO2 or TiO2 film is ∼ 0.5 nm for each layer, before and after annealing treatment of 900 °C for 1 min in N2 ambient. High-resolution transmission electron microscopy, x-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy measurements on high-k HfO2/TiO2 multilayers confirm the layer-by-layer structure after annealing treatment, suggesting the HfO2/TiO2 multilayer quantum wells. The valence band offsets of HfO2 and TiO2 films are found to be ∼ 3.1 and ∼ 1.5 eV, respectively. The conduction band offsets are found to be ∼ 1.7 eV for HfO2 films and ∼ 0.9 eV for TiO2 films. The high-k HfO2/TiO2 multilayers in p-Si/SiO2/(HfO2/TiO2)/Al2O3/aluminum memory capacitor show a large capacitance-voltage hysteresis memory window of ∼ 5 V at gate voltage of ±5 V, due to the charge storage in multilayer quantum wells. The hysteresis memory window of ∼ 1.3 V at small gate voltage of ±1 V is also observed. The high-k HfO2/TiO2 multilayer memory structure can be used in future nanoscale flash memory device applications.