There is an increasing interest in the fabrication of cement-based materials via additive manufacturing (AM) techniques. However, the processing-induced heterogeneities and interfaces represent a major challenge. The role of processing in creating interfaces and their characteristics requires understanding of the microstructure of 3D-printed hardened cement paste (hcp). This work investigates the microstructural features of architectured cement-based materials, including processing-induced heterogeneous patterns, interfacial regions (IRs), and pore network distributions with respect to the architectural patterns. A 3D printer was modified and merged with an extrusion system and specimens were 3D-printed using a layer-wise direct ink writing (DIW) process capable of fabrication of ‘lamellar’ architectures of materials. A lab-based X-ray microscope (XRM) was used to perform X-ray micro-computed tomography (micro-CT) evaluations to explore the microstructural characteristics of 3-day old intact (i.e. not tested) 3D printed and cast specimens at two levels of magnification: 0.4X and 4X. CT scans of printed specimen revealed a patterned pore network and several microstructural features, including: (a) macropores (visible during printing), (b) micropores at interfacial regions (IRs), (c) accumulation of anhydrous cement particles near macropores, and (d) rearrangement of filaments away from their designed toolpath. In comparison, microstructural investigation of cast specimen at 4X scan revealed randomly distributed pores with no connectivity throughout the specimen. The aptitude of micro-CT as a non-destructive technique for microstructural characterization of architectured cement-based materials is discussed. The role of processing to induce and to pattern heterogeneities such as IRs in materials is demonstrated and the role of architecture in controlling such heterogeneities and their directionality through the interface is discussed.