While electrospinning provides an excellent preparation method for the manufacturing of polymer fibers with defined diameter, controlling the overall porosity of the resulting fiber assemblies has remained elusive, particularly at higher porosities. In this study, the use of a low-temperature fiber collection device in air with controlled humidity allowed the simultaneous deposition of polymer fibers and ice particles from condensing humidity. The ice particles were intimately embedded within the polymer fibers and served as a pore template thus defining the mesh porosity after drying of the collected fiber assemblies. The amount of water condensation therefore contributes to the control of the mean interfiber distance and the resulting porosity. This simple and well accessible use of ice crystals as void templates gives access to the preparation of biodegradable tissue engineering scaffolds with an up to four times higher porosity if compared to conventional fiber electrospinning. The successful application of low-temperature electrospinning using polyesters or polyurethanes suggests a broad, material independent applicability of the process for the preparation of highly porous polymer structures. POLYM. ENG. SCI., 47:2020–2026, 2007. © 2007 Society of Plastics Engineers