Slippery liquid-infused porous surfaces (SLIPS) have potential impact on a wide range of industries, including healthcare, food packaging, and automobile. A tremendouseffort has been focused on developing novel fabrication methods for making SLIPS. However, current fabrication methods usually involve harsh conditions and complicated postfabrication modifications or are limited to specific substrates. Presented here is a novel method for the fast and facile fabrication of SLIPS. Layer-by-layer (LBL) assembly of branched polyethylenimine and Nafion, a perfluorinated polyelectrolyte, is performed with methanol as the solvent. Hierarchically rough and superhydrophobic surface is obtained directly without further modification on various substrates. The surface properties are shown to highly depend on the LBL assembly parameters, including deposition cycles, dipping time, rinsing time, and drying time between baths. The polyelectrolyte multilayers obtained with this method are infused with Krytox 100 to form SLIPS surfaces, which show excellent omniphobic, antifouling, self-cleaning, flexible, and optical properties. The result of this study not only simplifies the fabrication of SLIPS surfaces, but also provides great insight for making LBL films with specific morphologies.