A photocrosslinkable poly(ε-caprolactone) (PCL)-based resin was developed and applied using stereolithography. No additional solvents were required during the structure preparation process. Three-armed PCL oligomers of varying molecular weights were synthesized, functionalized with methacrylic anhydride, and photocrosslinked, resulting in high gel content networks. Stereolithography was used to build designed porous scaffolds using the resin containing PCL macromer, Irgacure 369 photoinitiator, inhibitor and dye. A suitable resin viscosity was obtained by heating the resin during the curing process. The scaffolds precisely matched the computer-aided designs, with no observable material shrinkage. The average porosity was 70.5 ± 0.8%, and the average pore size was 465 μm. The pore network was highly interconnected. The photocrosslinkable, biodegradable PCL resin is well suited for the solvent-free fabrication of tissue engineering scaffolds by stereolithography.