The potential in a synaptic simulation for neuromorphic computation has revived the research interest of resistive random access memory (RRAM). However, novel applications require reliable multilevel resistive switching (RS), which still represents a challenge. We demonstrate in this work the achievement of reliable HfO 2 -based RRAM devices for synaptic simulation by performing the Al doping and the postdeposition annealing (PDA). Transmission electron microscopy and operando hard X-ray photoelectron spectroscopy results reveal the positive impact of Al doping on the formation of oxygen vacancies. Detailed I−V characterizations demonstrate that the 16.5% Al doping concentration leads to better RS properties of the device. In comparison with the other reported results based on HfO 2 RRAM, our devices with 16.5% Aldoping and PDA at 450 °C show better reliable multilevel RS (∼20 levels) performance and an increased on/off ratio. The 16.5% Al:HfO 2 sample with PDA at 450 °C shows good potentiation/depression characteristics with low pulse width (10 μs) along with a good On/Off ratio (>1000), good data retention at room temperature, and high temperature and good program/erase endurance characteristics with a pulse width of 50 ns. The synapse features including potentiation, depression, and spike time-dependent plasticity were successfully achieved using optimized Al-HfO 2 RRAM devices. Our results demonstrate the beneficial effects of Al doping and PDA on the enhancement of the performances of RRAM devices for the synaptic simulation in neuromorphic computing applications.