Encapsulation of a hydrophobic guest molecule inside a micelle and its stimuli-sensitive release is a useful strategy for target-specific drug delivery. Herein, nine biobased glycolipids were derived from plant sources. The influence of headgroup on the stability and aggregation pattern in water with different alkyl chain lengths was investigated to deduce the structure property relationship. External factors, such as temperature, pH, and NaCl and urea. concentrations, were employed to explore stimuli response of glycolipid nanoassemblies. Furthermore, solvatochromic dyes, such as pyrene, N-phenyl-1-naphthylamine, and curcumin, were utilized to examine hydrophobe loading capacities of these glycolipid assemblies. A fluorescence study was performed to investigate the enzyme-sensitive hydrophobe release. Interestingly, the pH-sensitive hydrophobic guests showed pH-responsive release from dynamic micelles. Finally, the synthesized glycolipids revealed their nanoassemblies as smart carriers for hydrophobic cargo.