Chemical etching, liquid phase deposition, and dipping techniques were utilized to fabricate highly hydrophobic micro- and nanoscale coating surfaces on stainless-steel substrates. Heat transfer and fouling characteristics on these surfaces in pool boiling of deionized water and CaSO4 solution were studied. High roughness and hydrophobicity of coated surfaces were obtained on chemically etched substrates. Compared to the polished stainless-steel surface, the chemically etched coating surface provided a three times enhanced nucleate boiling coefficient at high heat flux. Obvious decrease of CaSO4 fouling resistance was obtained on chemically etched surfaces due to the higher roughness and hydrophobicity before the fouling resistance reaches the asymptotic value. Slightly high asymptotic fouling resistance was observed compared with coating surfaces without chemical etching of substrates.