Positional ordering, patterning, and crystallographic structuring of materials are requisite for device fabrication at the nano/ microscale. Template-directed capillary assembly of colloidal particles [1] precisely controls the placement of nano/microscale objects into surface patterns for the generation of nano/microarrays and colloidal superstructures. [2][3][4][5] The method entails evaporation of particle suspensions comprised of polymer colloids, [6][7][8][9][10] metallic nanoparticles, [11][12][13][14][15][16][17][18] or biomolecules [19][20][21] onto rigid or elastomeric substrates patterned with ordered cavities. Both 2D and 3D microarrays and colloidal clusters ensue with potential uses as optical materials, photonic bandgap structures, sensors, and substrates for epitaxial growth of more complex colloidal materials.The scope of surface patterns that can be produced with techniques such as photolithography, soft lithography, and electron beam lithography, enables precise control of geometry and organization of nano/micro-objects. Using these techniques, particles can either be deposited individually with Capillary assembly is a versatile method for depositing colloidal particles within templates, resulting in nano/microarrays and colloidal superstructures for optical, plasmonic, and sensory applications. Liquid particles (LPs), comprised of oligomerized 3-(trimethoxysilyl)propyl methacrylate, are herein shown to deposit into patterned cavities via capillary assembly. In contrast to solid colloids, LPs coalesce upon solvent evaporation and assume the geometry of the template. Incorporating small molecules such as dyes followed by LP solidification generates fluorescent polymer microarrays of any geometry. The LP size is inversely proportional to the quantity of deposited material and the convexity of the final polymer array. Cavity filling can be tuned by increasing the assembly temperature. Extraction of the polymerized regions produces solidified particles with faceted shapes including square prisms, trapezoids, and ellipsoids with sizes up to 14 µm that retain the shape of the cavity in which they are initially held. LP deposition thus presents a highly controllable fabrication scheme for geometrically diverse polymer microarrays and anisotropic colloids of any conceivable polygonal shape due to space filling of the template. The extension of capillary assembly to LPs that can be doped with small molecule dyes and analytes invaluably expands the synthetic toolbox for top-down, scalable, hierarchically engineered materials. www.advancedsciencenews.com