Current thoroughly described biodegradable and cross‐linkable polymers mainly rely on acrylate cross‐linking. However, despite the swift cross‐linking kinetics of acrylates, the concomitant brittleness of the resulting materials limits their applicability. Here, photo‐cross‐linkable poly(ε‐caprolactone) networks through orthogonal thiol‐ene chemistry are introduced. The step‐growth polymerized networks are tunable, predictable by means of the rubber elasticity theory and it is shown that their mechanical properties are significantly improved over their acrylate cross‐linked counterparts. Tunability is introduced to the materials, by altering Mc (or the molar mass between cross‐links), and its effect on the thermal properties, mechanical strength and degradability of the materials is evaluated. Moreover, excellent volumetric printability is illustrated and the smallest features obtained via volumetric 3D‐printing to date are reported, for thiol‐ene systems. Finally, by means of in vitro and in vivo characterization of 3D‐printed constructs, it is illustrated that the volumetrically 3D‐printed materials are biocompatible. This combination of mechanical stability, tunability, biocompatibility, and rapid fabrication by volumetric 3D‐printing charts a new path toward bedside manufacturing of biodegradable patient‐specific implants.

Thiol–ene photo-crosslinked poly-ε-caprolactone networks, exhibiting varying network architectures, were employed to fine-tune physico-chemical characteristics, while simultaneously exploring their potential application in digital light processing.

Volumetric 3D Printing In volumetric 3D printing, the whole 3D object is developed simultaneously (i.e., volume‐at‐once) by means of light‐induced crosslinking of a (rotating) liquid resin, as reported by Sandra Van Vlierberghe and co‐workers in article number 2210136. The 3D‐structure illustrated in the image is based on the chemical network structure of the reported thiol–ene crosslinked poly(caprolactone) (PCL) network, which can be considered a homogeneous 3D network consisting of telechelic alkene‐functionalized PCL and tetra‐functional thiol crosslinker junctions.