The effect of the TiW barrier layer on the switching properties of Ga-doped ZnO (GZO) nanorods based on Electrochemical Metallization Memory is investigated. Vertically wellaligned and uniform GZO nanorods having a diameter of approximately 35 nm are hydrothermally grown on a seeding layer of ZnO deposited on indium tin oxide (ITO) coated glass substrate, to fabricate Cu/TiW/nanorods/ITO/Glass devices. The remarkable enhancement in the memory window (on/off ratio) is achieved in the 5 nm TiW barrier layer embedded device. This device exhibits endurance of more than 103 cycles and a large memory window of ~103. The conduction mechanism at different current regions is studied, and it is found that Schottky emission is dominated in the low field region. The TiW barrier layer helps to retain the Cu ions and control the Cu ions diffusion, hence control the filament growth into the resistive layer, confirmed from the X-ray photoelectron spectroscopy (XPS) analysis. This device is suitable for the future low power non-volatile memory devices.