The complex structures and functional material systems of natural organisms effectively cope with crisis-ridden living environments such as high temperature, drought, toxicity, and predator. Behind these excellent survival strategies evolved over hundreds of millions of years is a series of effective mechanical, optical, hydraulic, and electromagnetic properties. Bionic design and manufacturing have always attracted extensive attention, but the progress has been limited by the inability of traditional manufacturing techniques to reproduce microscopically complex structures and the lack of functional materials. Therefore, there is an urgent need for a fabrication technique with a high degree of fabrication freedom and using composites derived from biological materials. Vat photopolymerization, an emerging additive manufacturing (aka 3D printing) technology, exhibits high manufacturing flexibility in the integrated manufacturing of multi-material systems and multi-scale structures. Here, biomaterial-inspired heterogeneous material systems based on polymer matrices and nanofillers, the introduction of electric field on the basis of conventional 3D printing systems, electrically assisted vat photopolymerization (E-VPP), to spatially and programmably distribute nanofillers are summarized, which provides a new strategy for fabricating anisotropic structures. The application of this versatile 3D printing system in 1) fabricating superhydrophobic structures with controllable micro/nano dual scale surface roughness, 2) dynamically aligning non-conductive nanofiller under electric field using liquid crystal templating, 3) creating hygro-responsive structures with anisotropic gradient porosity, and 4) manufacturing polymer/metal structure in a single step with photocurable heterogeneous material are extensively elaborated.