AbstractMemristive devices with valence change mechanism (VCM) show promise for neuromorphic data processing, although emulation of synaptic behavior with analog weight updates remains a challenge. Standard filamentary and area‐dependent resistive switching exhibit characteristic differences in the transition from the high to low resistance state, which is either abrupt with inherently high variability or gradual and allows quasi‐analog operation. In this study, the two switching modes are clearly correlated to differences in the microstructure and electronic structure for Pt/Al₂O₃/TiO_x/Cr/Pt devices made from amorphous layers of 1.2 nm Al₂O₃ and 7 nm TiO_x by atomic layer deposition. For the filamentary mode, operando spectromicroscopy experiments identify a localized region of ≈50 nm in diameter of reduced titania surrounded by crystalline rutile‐like TiO₂, highlighting the importance of Joule heating for this mode. In contrast, both oxide layers remain in their amorphous state for the interfacial mode, which proves that device temperature during switching stays below 670 K, which is the TiO₂ crystallization temperature. The analysis of the electronic conduction behavior confirms that the interfacial switching occurs by modulating the effective tunnel barrier width due to accumulation and depletion of oxygen vacancies at the Al₂O₃/TiO_x interface. The results are transferable to other bilayer stacks.