AbstractMethods suitable for formation of polyester nano‐ and microspheres with controlled surface properties are described. The title nano‐ and microspheres composed of polylactides or poly(ϵ‐caprolactone) were obtained either directly, during dispersion polymerization of corresponding monomers, or by self‐assembly of block copolymers containing polyester blocks. Surface properties of the particles were controlled by using surfactants with required functional groups for dispersion polymerization, by modification of interfacial layer of synthesized particles, and by using for self‐assembly copolymers with appropriate functional groups. Particles with alkyl, amino, hydroxyl, carboxyl, and 4‐(phenyl‐azo)phenyl groups in interfacial layer were obtained. Stability of suspensions of particles and particle's integrity did depend on the nature of functional groups in their interfacial layer and on external stimuli such as pH of suspending medium and irradiation with UV light.