Micro/nanostructured wicking surfaces with different submicron-scale substructures were fabricated by using electrochemical deposition and chemical etching methods on stainless steel spheres. Quenching experiments were carried out on these surfaces in saturated water to reveal the effect of submicron-scale substructures on the boiling heat transfer enhanced by wickability. The results indicated that, as compared to the knife-like submicron-scale substructure, the needle-like substructure improved the wickability of wicking surface, but has a weaker boiling heat transfer enhancement. The difference in wicking/spreading performance between two wicking surfaces with different submicron-scale substructures could not be enough to significantly affect the boiling heat transfer during quenching. However, the knife-like substructure might have a larger specific surface area, resulting in a greater boiling heat transfer enhancement. Besides, liquid spreading distance measured at room temperature might not be suitable for the wickability characterization.