Poly(L-lactide-co-ε-caprolactone) (PLCL) has emerged as a promising biocompatible copolyester, offering excellent structural flexibility alongside tunable shape-memory properties for advanced biomedical applications. However, its substantial crystallizable amorphous fraction makes it highly susceptible to cold crystallization during powder-bed preheating and laser-induced thermal cycling, resulting in severe powder caking and part warpage during laser powder bed fusion (LPBF). Herein, thermal annealing was used to reduce the crystallizable amorphous fraction available for cold crystallization of PLCL microspheres. Systematic evaluation revealed that annealing at 120 °C for 1 h nearly eliminated the cold-crystallization peak and increased XRD-derived crystallinity of the PLCL microspheres from 34.9% to 47.1%. Meanwhile, the annealed powder retained sufficient elevated-temperature mobility to support stable recoating at a nominal powder-bed preheating temperature of 100 °C, successfully mitigating part warpage during LPBF. At a selected volumetric energy density of 0.37 J/mm³, the printed specimens exhibited an apparent porosity of 11.7 ± 0.4%, a tensile modulus of 206.62 ± 61.39 MPa, and a tensile strength of 5.91 ± 0.72 MPa. The elongation at break reached approximately 180% at 37 °C. As a proof of concept, a PLCL scaffold with a triply periodic minimal surface (TPMS) architecture containing curved and overhanging features was successfully fabricated. These results support thermal annealing as a feasible pretreatment strategy for the LPBF processing of PLCL microspheres and provide a basis for future studies of temperature-responsive PLCL scaffolds.