Simultaneous 3D printing of disparate materials; metals, polymers and semiconductors with device quality interfaces and at high resolution remains challenging. Moreover, the precise placement of discrete and continuous domains to enable both device performance and electrical connectivity poses barriers to current high-speed 3D-printing approaches. Here, we report filaments with disparate materials arranged in elaborate microstructures, combined with an external adhesion promoter, to enable a wide range of topological outcomes and device-quality interfaces in 3D printed media. Filaments, structured towards light-detection, are printed into fully-connected 3D serpentine and spherical sensors capable of spatially resolving light at micron resolution across its entire centimeter-scale surface. 0-dimensional metallic microspheres generate light-emitting filaments that are printed into hierarchical 3D objects dotted with electroluminescent pixels at high device resolution of 55 µm not restricted by surface tension effects. Structured multimaterial filaments provides a path towards custom three-dimensional functional devices not realizable by existing approaches.