Dendritic core–shell architectures containing poly (glycerol) and poly (ethylene imine) cores and poly(lactide) shell (PG-PLA and PEI-PLA respectively) were synthesized. Analogous of these core–shell architectures containing the same cores but poly (L-lactide) shell (PG-PLLA and PEI-PLLA, respectively) were also synthesized. In this work PG and PEI were used as macroinitiator for ring opening polymerization of the lactid and L-lactide monomers. Different molar ratios of monomer to end functional groups of PG ([LA]/[OH]) and PEI ([LA]/[NHn] (n = 1 or 2)) were used to prepare the core–shell architectures with different shell thickness. These core–shell architectures were able to encapsulate and transport the small guest molecules. Their transport capacity (TC) depended on the type and thickness of the shells. TC of core–shell architectures containing PLLA shell was higher than that for their analogs containing PLA shell. The diameter of core–shell architectures was between 20–80 nm. The rate of release of guest molecules from chloroform solution of nanocarriers to water phase was investigated and it depended on the type of the core, shell and solvent.