This work evaluates the influence of the Ti/HfO₂ thickness ratio on the resistive switching (RS) performance of Ti/HfO₂-based memristors operating as Valence Change Memory (VCM). The RS mechanism in VCM devices is governed by electrochemical redox reactions and the electric field-assisted migration of oxygen anions, which induces local changes in the oxide stoichiometry and lead to the formation of an oxygen-deficient conductive filament (CF) [1]. The fabricated memristors consist of TiN/Ti/HfO2/W structures in a cross-point configuration, with varying Ti-to-HfO₂ thickness ratios (tTi/tHfO₂) and a device size of 25 µm² (Fig. 1). The optimal thickness of the Ti oxygen-scavenging layer is directly related to the thickness of the switching oxide layer. Understanding the reason behind this behavior is crucial for enhancing the performance, reliability, and stability of VCM systems. Electrical characterization (Fig.2) reveals that the best performance, in terms of C2C variability and enhanced memory window, is achieved for tTi/tHfO2 values close to 1. In contrast, a lower thickness ratio (tTi/tHfO2 = 0.25) limits oxygen availability, decreasing the efficiency of redox reactions and consequently degrading the device performance during the RS process. Furthermore, a statistical analysis of the experimental data was performed using the fitdistrplus package within the R programming environment (Fig. 3) [2]. The results were integrated into SPICE simulations based on the Dynamic Memdiode Model, that focuses on the low and high current states without explicitly modeling transition details. This approach effectively captures the C2C variability of the analyzed devices.