Wettability tailoring of patterned silicon surface has great potential in fields producing integrated circuits, solar cells, sensors, detectors, and micro/nano electromechanical systems. The present paper presents a convenient yet effective method of combining reactive ion etching and catalyzed etching to prepare silicon surface with micro–nano dual-scale pillars. The experimental results indicate that the hydrophilic surface transformed to a superhydrophobic surface when micro–nano dual-scale pillars were formed. The surface preserved superhydrophobicity even when the geometric parameters of the micropillars were changed. Overhangs of water drops on steep micro–nano dual-scale pillars result in superhydrophobicity. This method offers a new way for tailoring the wettability of patterned silicon surfaces.