W. Kee Ng, Carlos T. B. Paula, Arménio C. Serra, Jorge F. J. Coelho, Paulo Jorge Bartolo
Abstract Vat photopolymerization (VP)‐based bioprinting is rapidly emerging as a transformative platform for fabricating complex, cell‐laden tissue constructs with unparalleled spatial resolution and geometric precision. This review presents a comprehensive overview of recent advances in VP‐based bioprinting, organized around core themes of photopolymerization chemistry, printing modalities, bio‐ink design, and biomedical applications. We first describe the underlying crosslinking mechanisms including chain‐growth, step‐growth, redox‐mediated, and initiator‐free systems that enable spatiotemporal control over polymerization. The discussion then moves to key VP‐based bioprinting techniques such as stereolithography apparatus (SLA), digital light processing, two‐photon polymerization, and volumetric additive manufacturing, emphasizing their printing principles and suitability for bioprinting applications. A central focus is placed on the rational design of photo‐crosslinkable bio‐inks, comprising functional monomers, photo‐initiators (PIs), and photo‐absorbers (PAs). We critically examine design criteria such as cytocompatibility, rheological and optical behavior, mechanical performance, degradation profiles, and scalability, highlighting the complex trade‐offs between print fidelity and biological function. The utility of VP‐based bioprinting is further illustrated through its application in constructing advanced tissues, including bone, cardiac, cartilage, corneal, and hepatic models. Finally, we explore emerging frontiers such as multi‐material and multi‐modal bioprinting, machine learning‐guided optimization, and regulatory pathways toward clinical translation. Collectively, these insights outline a roadmap for advancing VP‐based bioprinting into a clinically viable, high‐throughput tissue engineering technology.