Improving hydrophobicity through the regulation of surface microstructures has attracted significant interest in various applications. This research successfully prepared a surface with microsphere structures using the Non-solvent induced phase separation method (NIPS). Poly(D-Lactic acid)-block-poly(ethylene glycol)-block-poly(D-Lactic acid) (PDLA-PEG-PDLA) block polymers were synthesized by ring-opening polymerization of D-Lactic acid (D-LA) using polyethylene glycol (PEG) as initiator. PLLA/PDLA-PEG-PDLA membrane with microscale microsphere morphology was fabricated using a nonsolvent-induced self-assembly method by blending the triblock copolymer with a poly(L-lactic acid) (PLLA) solution. In phase separation processes, the amphiphilic block copolymers self-assemble into micellar structures to minimize the Gibbs free energy, and the hydrophilic segments (PEG) aggregate to form the core of the micelles, while the hydrophobic segments (PDLA) are exposed on the outer corona resulting in a core-shell structure. The Stereocomplex Crystalline (SC), formed by the hydrogen bonding between PLLA and PDLA, can facilitate the transition from liquid-liquid phase separation to solid-liquid phase separation, and the PEG chain segments can enhance the formation of SC. The membrane, prepared by adjusting the copolymer content and PEG chain length, exhibited adjustable microsphere quantity, diameter, and surface roughness, enabling excellent hydrophobicity and controlled release of oil-soluble substances.