Vat photopolymerization 3D printing provides new opportunities for the fabrication of tissue scaffolds and medical devices. However, for the manufacturing of biodegradable elastomers, it usually requires the use of organic solvents to dissolve the solid photoinitators and achieve low resin viscosity, making this process environmentally unfriendly and not optimal for biomedical applications. Here, we report solvent-free 3D printing of biodegradable elastomers by digital light processing with well-defined photoinitiator-polymer conjugates. Being in liquid state at room temperature, the macrophotoinitiators enabled high-quality 3D printing in the absence of any organic solvents that are usually used in digital light 3D printing. This allowed the systematic investigation of structure-property relationships of 3D-printed biodegradable elastomers without the interference from reactive diluents. The developed macrophotoinitiators were compatible with various photopolymers and could be applied for solvent-free fabrication of biodegradable shape-memory devices. This work offers new perspectives for the solvent-free additive manufacturing of bioresorbable medical implants and other functional devices.