The ever-increasing requirements of photosensitive materials are put forward by the increase in the applications of photocuring 3D printing in high-tech fields. Nevertheless, the poor compatibility between high-performance resins and photocurable monomers renders challenges associated with the preparation of solvent-free resins with excellent comprehensive properties. In this work, a maleimide oligomer with a noncoplanar branched structure is synthesized in one step, which can be dissolved in a photocurable monomer. A low-viscosity, high-performance photocurable resin is prepared without an organic solvent and printed in layer by layer into a high-resolution (50 µm) three-dimensional complex shape. The material’s crosslinking density is further increased by thermal curing, achieving a improvement in mechanical properties. The printing device exhibits an storage modulus of up to 1.9 GPa at 200 °C and a dimensional shrinkage of less than 4%; it can also support a heavy object that exceeds its own weight by 1124 times. This resin achieves the balance between the viscosity, printing accuracy, and performance, demonstrating immense application potential in microelectronics, aerospace, etc.