Superhydrophobic surfaces have received much attention due to their novel aspects of surface physics and important applications ranging from self-cleaning materials to microfluidic devices. Taking their inspiration from the self-cleaning property of lotus leaves [1] and insects, [2] the biomimetic results reveal that the synergistic interaction of the hierarchical micro-and nanostructure can not only improve the surface hydrophobicity but also reduce the sliding angle (SA), which is crucial to the self-cleaning properties of these surfaces.[3] Many efforts, including electrodeposition, polymer-phase separation, sol-gel methods, and others have been carried out to develop hierarchical micro-and nanostructures to obtain superhydrophobic surfaces. [4][5][6] Layer-by-layer self-assembly (LbL), which is based on the alternating physisorption of oppositely charged building blocks, represents a method to immobilize polyelectrolytes, colloid nanoparticles, and biomacromolecules, such as enzymes, extracellular matrices (ECM), DNA, etc. [7][8] The sensitivity of the LbL multilayer towards its environment (pH, ionic strength, etc.) further provides new approaches to adjust the layered nanostructure with a tailored composition and architecture. Recently, the use of the LbL technique for constructing superhydrophobic coatings has been explored. [9][10][11][12] Shiratori and co-workers [9] first constructed multilayered films containing SiO 2 nanoparticles, which were further heated to 650°C to develop an inorganic nanostructure for superhydrophobic behavior. Zhang and co-workers [10] reported the use of polyelectrolyte multilayers as a matrix for electrochemical deposition to adjust the topography of gold and silver clusters, leading to superhydrophobic surfaces. Rubner and co-workers [11] mimicked the superhydrophobic behavior of the lotusleaf structure by creating a microporous polyelectrolyte multilayer surface over-coated with silica nanoparticles. Schlenoff and co-workers [12] created an ultrahydrophobic surface roughening on both the micrometer and nanometer scale using layer-by-layer deposition of clay and fluorinated polyelectrolytes. Most of these methods, however, developed hierarchical micro-and nanostructures by combining the multiple assembly steps and different self-assembling building blocks, such as polyelectrolytes, metals, and nanoparticles. Herein, we report the amplified exponential growth of a multilayer of polyelectrolytes as a facile method to construct hierarchical micro-and nanostructures simultaneously, which can be further transformed into superhydropobic surfaces. The 3-aminopropyltriethoxysilane-coated substrates were alternately immersed in an aqueous solution of poly(acrylic acid) (PAA, 3 mg mL -1