Stereocomplex formation was revealed between two PLA-like oligoester enantiomers. Two oligomeric enantiomers of each alpha-hydroxyisovaleric acid and lactic acid were synthesized and two part blends were prepared between all oligomer combinations. The blends were evaluated by DSC and XRD and a new crystal structure was detected in the case of DIE. oligo-alpha-hydroxyisovaleric acid blend confirming stereocomplexation. Stereocomplexation was also verified for the D/L oligolactic acid blend. The two stereocomplexes had higher melting temperatures and increased enthalpy of melting compared to the pure oligomers. Hetero-stereocomplexation between different enantiomers of oligo(alpha-hydroxyisovaleric) acid and oligo(lactic acid) did not take place. The hydrolytic degradation rate was slower for the blends containing the more bulky and hydrophobic oligo(alpha-hydroxyisovaleric acid)s. Modifying PLA with this monomer could be used to reduce the degradation rate and at the same time modify the physical properties of PLA materials. (C) 2013 Elsevier Ltd. All rights reserved.