Optimized Photoclick (Bio)Resins for Fast Volumetric Bioprinting

Volumetric printing (VP) is a light‐mediated technique enabling printing of complex, low‐defect 3D objects within seconds, overcoming major drawbacks of layer‐by‐layer additive manufacturing. An optimized photoresin is presented for VP in the presence of cells (volumetric bioprinting) based on fast thiol–ene step‐growth photoclick crosslinking. Gelatin‐norbornene (Gel‐NB) photoresin shows superior performance, both in physicochemical and biocompatibility aspects, compared to (meth‐)acryloyl resins. The extremely efficient thiol–norbornene reaction produces the fastest VP reported to date (≈10 s), with significantly lower polymer content, degree of substitution (DS), and radical species, making it more suitable for cell encapsulation. This approach enables the generation of cellular free‐form constructs with excellent cell viability (≈100%) and tissue maturation potential, demonstrated by development of contractile myotubes. Varying the DS, polymer content, thiol–ene ratio, and thiolated crosslinker allows fine‐tuning of mechanical properties over a broad stiffness range (≈40 Pa to ≈15 kPa). These properties are achieved through fast and scalable methods for producing Gel‐NB with inexpensive, off‐the‐shelf reagents that can help establish it as the gold standard for light‐mediated biofabrication techniques. With potential applications from high‐throughput bioprinting of tissue models to soft robotics and regenerative medicine, this work paves the way for exploitation of VPs unprecedented capabilities. Volumetric printing enables the generation of centimeter‐sized free‐form 3D objects within seconds. Optimized photoclick‐based photoresins show ideal biophysical and photochemical properties resulting in fast and biocompatible volumetric bioprinting. Thiol–norbornene photo‐crosslinking outperforms chain‐growth systems permitting significant reduction of radical generation and polymer concentration. This simple and scalable synthesis method opens new avenues for widespread use of photoclick resins in light‐mediated biofabrication.