<p>Poly(ethylene succinate) (PES), a promising biodegradable polyester with cost advantages, suffers from inherently slow crystallization kinetics, which severely limits its processability and practical applications. To address this challenge, this study explored the use of commercially available, low-cost, and food-safe sugar alcohols, including Xylitol (Xy), D-sorbitol (DS), and D-mannitol (DM), as effective nucleating agents for PES. Remarkably, all three polyols significantly enhanced the nucleation and crystallization ability of PES, with DM exhibiting the most pronounced effect. DM increased the crystallization temperature by up to 23.9 °C and accelerated the overall crystallization rate by more than 13-fold at only 0.5 wt% loading level. Through a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD) analyses, we revealed that DM promotes PES crystallization <i>via</i> a dual mechanism: epitaxial templating facilitated by excellent lattice matching, and enhanced chain adjustment through intermolecular hydrogen-bonding interactions. In contrast, Xy and DS primarily function through hydrogen-bonding interactions. This work not only identifies DM as a highly efficient, economical, and industrially viable nucleating agent for PES, but also provides fundamental insights into the role of the molecular structure and crystallization ability of nucleating agents in regulating polymer crystallization.</p>