Near‐field electrospinning (NFES) holds the potential to develop into a versatile additive nanomanufacturing platform. However, the impact of a variety of processing variables remains unresolved.Herein, the effect of solvents used to prepare suitable solutions for 3D microstructuring by electrospinning is studied. 3D straight walls of stacked fibers are fabricated using a layer‐by‐layer fiber deposition approach. The effect of the choice of substrate material is also explored. The results show that a high vapor pressure, and a low dielectric constant of the solvent, as well as a high substrate conductivity facilitate improved stacking of fiber layers. Utilizing these conditions, 3D stacked walls of polyethylene oxide are fabricated, and a maximum aspect ratio of 191.7 ± 52.6, while using a chromium/gold substrate and dichloromethane/methanol as the solvent is achieved.