Porous polymer materials with interconnected porosity have recently received great attention due to their wide range of possible applications and the challenges they pose in preparation. Their potential applications range from use in the biomedical and pharmaceutical fields (tissue engineering and drug delivery) [1–3] to chromatographic materials, [4] to catalysis of chemical and biochemical reactions, [5] and to electronic devices. [6] For tissue-engineering applications, for instance, at least four different techniques for fabricating interconnected porous polymer substrates have been developed: fiber bonding of unwoven meshes, [7] solvent casting/particulate leaching, [8] gas foaming, [9] and phase separation. [10] However, every one of these approaches suffers from severe limitations including low levels of interconnectivity, low void volume, poor control of pore size and distribution, and difficulties in obtaining materials of reproducible porosities. Previously, we advanced an approach to preparing microporous materials based on the melt-blending of two immiscible polymers [11] and demonstrated that selective extraction of one of two components in a co-continuous mixture can result in a single-component structure of fully interconnected porosity with highly controlled porosity, morphology, and pore diameters ranging from 100 nm to hundreds of micrometers. [12,13] However, this method was found to be limited in the void volume that can be attained, and able to be used to prepare only relatively low-void-volume substrates (75%). Layer-by-layer (LbL) deposition is a simple and effective approach to deposit ultrathin and uniform molecular layers onto surfaces in which polyelectrolytes are adsorbed on an oppositely charged surface, reversing the surface charge and leaving it primed for the next deposition cycle. [14–16] Originally