Oxygen evolution reactions (OER) are highly significant and play a critical role in the advancement of fuel cells, electrolyzers, chemicals, and solar energy conversion devices. The challenge in the quest is attributed to the absence of an efficient electrocatalyst assembly that functions optimally. A simple method of electrodeposition of Al:WO3 on a fluorinated tin oxide (FTO) electrode was used to investigate the OER in this study. The electrodepositions were achieved by employing a three-electrode cell at various scan rates ranging from 10 to 100 mV/s. During this investigation, the influence of the scan rate on electrocatalyst loadings and the impact of electrocatalyst layer thickness on the OER were examined. The electrodepositions of Al:WO3@FTO were analyzed using a range of optical, chemical, and physical techniques such as SEM, XRD, FT-IR, Raman spectroscopy, EDX, EDS mapping, and electrochemical tests. The FTIR and Raman analysis confirmed the synthesis of AL:WO3 while the peaks detected at angles 38.7° and 43° by XRD with planes (111) and (200), served as a distinctive characteristic for identifying aluminum (Al). The peaks observed at angles of 27.8°, 30.7°, 33°, 50.45°, and 58° correspond to WO3 material. The characterization techniques also confirmed that the synthesized material is highly crystalline in nature. The OER potential using Al:WO3@FTO electrodes with different electrocatalyst thicknesses, ranging from 8 nm to 31 nm was investigated by studying various electrochemical techniques such as CV, LSV, CPE, Tafel slope, HP2P splitting, EIS, TOF, short and long-term electrode stability, and double layer capacitance. The linear regression coefficient (R2) was also calculated to measure the relationship between the electrocatalyst's thickness and each electrochemical test. The findings indicated that increasing the scan rates resulted in thinner and denser electrodepositions on the FTO substrate as the thinnest film was formed at 100 mV/s. An inverse relationship between electrocatalyst layer thickness and OER activity was observed. The electrode with the thinnest and most compact electrocatalyst layer, specifically ED Al:WO3@FTO08, exhibited the lowest onset potential of 1.48 V and a maximum current of 84 mA/cm2 at 1.76 V. It also demonstrated superior reaction kinetics, as evidenced by its lower Tafel slope value of 49 mV/dec, which is the lowest among all the electrodes that were prepared. In particular, the electrode with a thin and compact electrocatalyst layer worked better in OER operations than the other five electrodes that had higher amounts of Al:WO3.