In regards to the addition of functionality into polylactide, the chemical modification method is a promising approach. Herein, we selected 5-hydroxymethylfurfural (HMF) as the initiator to introduce the chain end of polylactide. HMF is a valuable biomass produced from glucose–fructose via dehydration. The structure of HMF contains aldehyde and alkyl alcohol, which resembles benzyl alcohol. This polymer was able to control the molecular weight. This meant that the polymerization initiated from HMF showed effective initiation for the polymerization, compared with vanillin in previous research. The present polymer improved the thermal properties by stereocomplex formation with both enantiomeric homopolymers. Subsequently, the terminal group of aldehyde of HMF undergoes bonding/removing as a dynamic formation with hydrophilic amine under equilibrium conditions. This phenomenon self-assembled interesting nanostructured morphology, and also, it was able to form a self-assembled monolayer (SAM). By using this S...