This paper reports a new method of functional metamaterial structure fabrication based on ultra-porous aerogel skins introduced on the surfaces of solid tetrakaidecahedron lattices obtained via 3D-printing tools. The solid tetrakaidecahedron lattice shapes are first fabricated from acrylate resin systems using a stereolithography printer. The lattice is then coated with a skin of polyimide gel via sol–gel reaction process, post-curing, and solvent-aging. The aerogel skin is recovered from the gel using supercritical drying. The lattice is found uniformly coated with polyimide aerogel skin as confirmed from examination of surface morphology via scanning electron microscopy and X-ray tomography imaging. The concept is extended to coatings by silica and Kevlar aerogel systems. The mechanical and thermal properties of the resultant materials and a set of applications are discussed.