Enzymatic polymerization is an environmentally benign process for the synthesis of biodegradable and biocompatible polymers. The regioselectivity of lipase B from Candida Antarctica (CAL-B) produces linear functional polyesters without protection-deprotection steps. In this work, two different methods for the enzymatic synthesis of functional polyesters based on renewable resources, as, e.g., glycerol, using CAL-B are outlined. Poly(glycerol adipate) was synthesized by enzymatic transesterification between glycerol and divinyl adipate or dimethyl adipate. Methods are also reported to graft poly(glycerol adipate) with different amounts of hydrophobic side chains (lauric, stearic, behenic, and oleic acids) and hydrophilic poly(ethylene glycol) side chains, respectively. The hydrophilicity or lipophilicity of grafted polyesters is well controlled by changing the degree of grafting of hydrophilic and hydrophobic side chains. The multiple grafted polyesters are characterized by NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and X-ray diffraction. Furthermore, the self-assembly of the graft copolymers in water and their use as steric stabilizers for cubosomes are discussed. For this purpose mainly dynamic light scattering and small angle X-ray scattering have been employed.