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 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. Specifically, 1) E-VPP can be used to control the surface roughness of Salvinia-like structures at the micro- and nano- scale through the introduction of multiwalled carbon nanotubes (MWCNTs). Experimental results show that the use of MWCNTs increases the superhydrophobic properties of these structures at a relatively high concentration compared to the normal pure resins. Alignment of MWCNTs also boosts overall performance in these biomimetic structures, such as mechanical strength, contact angle, and liquid surface attaching forces. 2) Liquid crystals can be used as a template or host medium to create microstructures in polymers in a process which is known as liquid crystal templating. It was found that the AC electric field responses are more consistent and maintain alignment better after the electric field is removed. The DC electric field responses were found to require less voltage and would achieve faster initial alignment results. DC electric field responses were found to be decreasing over a long period of time due to continual unidirectional flow from positive to negative electrodes. In conclusion, AC electric fields have more stable progressions of alignment, but DC electric fields align faster, with less applied voltage, and produce larger particle bundles. 3) Liquid crystal templating-assisted E-VPP can fabricate bioinspired porous structures with hygro-responsive capabilities by utilizing photopolymerization induced phase separation (PIPS) and liquid crystal (LC) electro-alignment. PIPS within the LC/nanofiller composites lead to the formation of sub-micron gradient porous structures after extracting nonreactive LCs. The electric field enables the programmable alignment of LCs, which in turn elongates the porous structures and aligns nanofillers. In addition, the programmable arranged nanofillers by the templated LCs enhance the degree of deformation and thus the resulting composites exhibit high shape control accuracy, fast dynamic response, and high reliability. 4) A novel manufacturing strategy to build bioinspired hierarchical structures with heterogeneous material systems using E-VPP. The photocurable printing solution that can act as an electrolyte for charge transfer was developed, and the curing characteristic of the printing solution was further investigated. A fundamental understanding of the formation mechanism of metallic structures on the polymer matrix was studied through physics-based multiscale modeling and simulations. The correlation between metallic structures morphology, printing solution properties, and printing process parameters, and their effects in building bioinspired hierarchical structures with heterogeneous materials were identified. Overall, E-VPP holds immense potential to revolutionize manufacturing by mimicking nature’s complex survival strategies, utilizing effective mechanical, optical, hydraulic, and electromagnetic properties and offers diverse applications in various fields, including self-sensing, motion tracking, energy harvesting, and soft actuating.