Melt electrowriting (MEW) is an additive manufacturing (AM) technique using thermoplastic polymers to produce microscale structures, including scaffolds for tissue engineering. MEW scaffolds have, in general, high porosities and can be designed with different fiber diameters, spacings, and laydown patterns. The need for a reliable method for scaffold characterization is essential for quality assurance and research purposes. In this study, we describe the use of submicrometer X-ray tomography for the generation of local thickness maps of volume porosity of 16 different scaffold groups, comprising 2 diameter groups, 2 fiber spacing groups, and 4 different laydown patters (0/90°, 0/60/120°, 0/45/90/135°, and 0/30/60/90/120/150°), all made using a custom-built MEW printer with medical-grade poly(ɛ-caprolactone). The results showed a porosity range between 77.7% and 90.7% for all the scaffolds. Moreover, the influence of the scaffold regularity and flatness in the more regular pore shapes (0/90°, 0/60/120°) lead to the shift of the local thickness graph to one side, and thus the prevalence of one pore size. This nondestructive method for MEW scaffold characterization overcomes the limitations of microscopic methods of pore shape and size estimation. Impact Statement Melt electrowriting is an AM technology that bridges the gap between solution electrospinning and melt microextrusion technologies. It can be applied to biomaterials and tissue engineering by making a spectrum of scaffolds with various laydown patterns at dimensions not previously studied. Using submicrometer X-ray tomography, a “fingerprint” of porosity for such scaffolds can be obtained and used as an important measure for quality control, to ensure that the scaffold fabricated is the one designed and allows the selection of specific scaffolds based on desired porosities.