The growing demand for advanced functional materials has led to the development of various additive manufacturing techniques (AM), with vat photopolymerization (VP) emerging as a key technology. VP is a versatile light‐based AM technique for producing complex 3D structures from a wide range of functional materials. VP material diversity stems from its compatibility with various monomers, oligomers, solvents, and fillers, enabling for the fabrication of materials with tailored properties. This article systematically examines recent advancements in VP fabrication and analyzes strategies for incorporating functional elements into 3D‐printed material structures. We investigate the spectrum of functionalities achieved in novel materials by categorizing design into four main groups: The use of functional additives, the molecular design of the photopolymerizable system, post‐processing procedures, and functional structural architectures. Specifically, we analyze recent reports on novel functional materials in the field of VP, such as conductive, energy‐storing, optical, high‐performance, stimuli‐responsive, self‐healing, shape‐memory, recyclable, bioengineering, and biomedical materials. The article also discusses characterization methods required for the fabrication of state‐of‐the‐art materials. We conclude by underscoring the immense versatility of VP for fabricating functional and multifunctional materials, and its potential for future advancements in applications such as energy, medicine, robotics, and physical AI.

Bucky gel electrodes are composed of morphology-determining polyvinylidene difluoride (PVDF) filled with carbon nanotubes (CNT). The electrodes are commonly fabricated via the casting of a CNT dispersion containing PVDF and ionic liquid. In this study, several pore-forming additives such as polyethylene glycol (PEG), dibutyl phthalate (DBP), and the common ionic liquid BMIMBF4 were used to control the morphology of the bucky gel electrodes. The crystalline phase type and content of PVDF in the electrodes were determined by FT-IR and DSC, respectively. SEM revealed a sponge-like structure in the case of the use of BMIMBF4 and a spherulite structure if PEG and DBP were used as additives. A strong influence of morphology on the anisotropic increase in the volume of electrodes upon impregnation with electrolyte was observed. The PEG-based electrode elongated more than the others, while the BMIMBF4-based electrode thickened to a greater extent. Ionic actuators were fabricated to experimentally reveal the effect of electrode morphology on their electromechanical efficiency. A high-precision vat photopolymerization technique was used to fabricate identical ionic membranes and minimize their influence on the properties of the actuators. The electrodes were characterized by the same porosity and electrical capacitance, while the actuators differ significantly in performance. As a result, a simple method of using pore-forming additives made it possible to increase the maximum deformation of bucky gel ionic actuators by 1.5 times by changing the morphology of the electrodes.