Nanostructured microporous surfaces were electrodeposited at various electrolyte temperatures on copper substrate to investigate the saturated pool boiling enhancement of distilled water at atmospheric pressure. Surface structure topography and wickability were analyzed to investigate their relation to critical heat flux. Scanning electron microscope showed that the micro-clusters have nanostructures from cubic at 5°C to dendritic at 60°C electrolyte temperature. Rate-of-rise experiments demonstrated that dendritic copper structure has the best capillary performance. The experimental results of pool boiling heat transfer indicate that the critical heat flux increased with surface wickability. Electrodeposited porous surface in hot electrolyte showed the highest critical heat flux and heat transfer coefficient of the 124 W/cm2 and 17 W/cm2K, respectively, which is 50% and 270% higher than that of plain surface. However, the two-step electrodeposition and annealing were used in fabrication of surfaces, but the mechanical strength of layer needs more improvement by changing the electrochemical process parameters.