Selective deposition and preferential alignment of two-dimensional (2D) nanoparticles on complex and flexible three-dimensional (3D) substrates can tune material properties and enrich structural versatility for broad applications in wearable health monitoring, soft robotics, and human−machine interfaces. However, achieving precise and scalable control of the morphology of layer-structured nanomaterials is challenging, especially constructing hierarchical architectures consistent from nanoscale alignment to microscale patterning to complex macroscale landscapes. This work demonstrated a scalable and straightforward hybrid 3D printing method for orientational alignment and positional patterning of 2D MXene nanoparticles. This process involved (i) surface topology design via microcontinuous liquid interface production (μCLIP) and (ii) directed assembly of MXene flakes via capillarity-driven direct ink writing (DIW). With well-managed surface patterning geometry and printing ink quality control, the surface microchannels constrained MXene suspensions and leveraged microforces to facilitate preferential alignment of MXene sheets via layer-by-layer additive depositions. The printed devices displayed multifunctional properties, i.e., anisotropic conductivity and piezoresistive sensing with a wide sensing range, high sensitivity, fast response time, and mechanical durability. Our fabrication technique shows enormous potential for rapid, digital, scalable, and low-cost manufacturing of hierarchical structures, especially for micropatterning and aligning 2D nanoparticles not easily accessible through conventional processing methods.