Complex 3D functional architectures are of widespread interest due to their potential applications in biomedical devices, [1][2][3][4][5] metamaterials, [6][7][8][9][10] energy storage and conversion platforms, [11][12][13][14][15][16] and electronics systems. [17][18][19][20][21][22][23] Although existing fabrication techniques such as 3D printing, [4,14,[24][25][26][27][28][29][30][31][32] templated growth, [33][34][35][36] and controlled folding [2,[37][38][39][40][41][42][43] can serve as powerful routes to diverse classes of 3D structures that address requirements in a number of interesting technologies, each has some set of limitations in materials compatibility, accessible feature sizes, and compatibility with well-developed 2D processing techniques used in the semiconductor and photonics industries. [44][45][46] Despite significant efforts in research and development, there remains a need for methods that provide access to complex 3D mesostructures that incorporate high-performance materials.Capabilities for controlled formation of sophisticated 3D micro/nanostructures in advanced materials have foundational implications across a broad range of fields. Recently developed methods use stress release in prestrained elastomeric substrates as a driving force for assembling 3D structures and functional microdevices from 2D precursors. A limitation of this approach is that releasing these structures from their substrate returns them to their original 2D layouts due to the elastic recovery of the constituent materials. Here, a concept in which shape memory polymers serve as a means to achieve freestanding 3D architectures from the same basic approach is introduced, with demonstrated ability to realize lateral dimensions, characteristic feature sizes, and thicknesses as small as ≈500, 10, and 5 µm simultaneously, and the potential to scale to much larger or smaller dimensions. Wireless electronic devices illustrate the capacity to integrate other materials and functional components into these 3D frameworks. Quantitative mechanics modeling and experimental measurements illustrate not only shape fixation but also capabilities that allow for structure recovery and shape programmability, as a form of 4D structural control. These ideas provide opportunities in fields ranging from micro-electromechanical systems and microrobotics, to smart intravascular stents, tissue scaffolds, and many others. www.advmat.de www.advancedsciencenews.com A collection of recent publications reports schemes that exploit compressive buckling as a means for assembly of complex 3D functional devices in a diversity of configurations and with a broad range of material compositions, including critical dimensions that span nanometer to centimeter length scales. [47][48][49][50][51] Here, relaxation of a prestrained elastomer substrate, as an assembly platform, imposes stresses on a 2D precursor structure to transform its geometry into a desired 3D shape. With a few exceptions, [52,53] deformations of the micro/ nanomaterials in the precursor rema...