Surfaces designed with specific wetting properties are still a key challenge in materials science. We present here a facile preparation of a surface assembled by the layer-by-layer technique, using a colloidal dispersion of ionomer particles and linear polyethylene imine. The colloidal ethylene-co-methacrylic acid (EMAA) particles are on the order of half a micron in size with surface features from 40 to 100 nm in width. The resultant surface has roughness on two length scales, one on the micron scale due to the packing of particles and one on the nanoscale due to these surface features on the EMAA particles. This hierarchical structure results in a hydrophobic surface with good water pinning properties (∼550 μN). We show that there is a balance between maximizing contact angle and water pinning force. Furthermore, this surface is oleophilic with regard to many organic solvents, also demonstrating underwater oleophobicity, and given the difference in wetting between aqueous and organic phases, this material may be a candidate material for oil/water separations.