Recent research has increased in eco-friendly hot-melt adhesives as alternatives to conventional commercial hot-melt adhesives. However, there have been limitations in terms of removability and biodegradability. This study addresses these issues by designing a novel molecular structure for a single polymer, resulting in a sustainable hot-melt adhesive that offers strong adhesion, clear removability, and high biodegradability without additional additives. By varying the ratio of alcohol monomers 1,4-butanediol (BD) and ethylene glycol (EG) during polymerization, we synthesized poly(butylene adipate-co-butylene terephthalate-co-ethylene adipate-co-ethylene terephthalate) (PBEAT) with four block segments. We increased the open time by reducing the regularity of the molecular structure, controlling crystallization behavior, and inhibiting polymer chain packing. This improvement in wettability with the adherend allowed us to achieve a lap shear adhesion strength of 3.18 MPa. Additionally, we proposed a debonding mechanism based on the correlation between the crystallization temperature (Tc) block copolymer's and shear adhesion failure temperature (SAFT), demonstrating the removability of the prepared hot-melt adhesive. Finally, analyses of hydrolysis, enzymatic degradation, and biodegradation in compost confirmed that reduced crystallinity enhances biodegradability. PBE30AT, exhibiting the strongest adhesion strength, achieves complete degradation in compost within 20 days, faster than neat poly(butylene adipate-co-terephthalate) (PBAT). This research offers a novel and practical approach to enhancing the potential and expandability of sustainable adhesives by tailoring the molecular structure of the polymer.