Enantiomeric diblock and triblock copolymers from caprolactone and lactide with various compositions were synthesized using alcohol/tin octoate as initiator system. Stereocomplexes were formed between pairs of enantiomeric block copolymers and their thermal properties examined. The melting temperatures of the crystalline PCL and PLA phases are depending on the composition of block copolymers. A raise of approximately 55 degreesC of the temperature of PLA phase is observed in the blends as a consequence of stereocomplex formation as well in diblock as in triblock copolymers.