ITO-based transparent conductive electrodes (TCE) with Ag/Ni thin metal under-layer were deposited on Si and glass substrates by thermal evaporator and RF magnetron sputtering system. Ceramic ITO with purity of 99.99% and In2O3:SnO2 weight ratio of 90:10 was used as a target at room temperature. Post-deposition annealing was performed on the TCE at moderate temperature of 500°C, 600°C and 700°C under N2 ambient. It was observed that the structural properties, optical transmittance, electrical characteristics and surface morphology were improved significantly after the post-annealing process. Post-annealed ITO/Ag/Ni at 600°C shows the best quality of TCE with figure-of-merit (FOM) of 1.5×10−2Ω−1 and high optical transmittance of 83% at 470nm as well as very low electrical resistivity of 4.3×10−5Ω-cm. The crystalline quality and surface morphological plays an important role in determining the quality of the TCE multilayer thin films properties.