In summary, we have successfully synthesized a series of homopolymers of chiral and racemic poly(2,4disubstituted-2-oxazoline)s, namely p R EtEtOx, p S EtEtOx, p RS EtEtOx, p R PrMeOx, p S PrMeOx and p RS PrMeOx via LCROP. Subsequently, novel ABA triblock copolymers were synthesized using these chiral and racemic hydrophobic p R EtEtOx, p S EtEtOx, p RS EtEtOx, p R PrMeOx, p S PrMeOx and p RS PrMeOx as block B and hydrophilic pMeOx as block A. The polymers were extensively characterized by 1 H-NMR spectroscopy, GPC, TGA, DSC and CD-spectroscopy. Attributable to the steric hindrance caused by the methyl/ethyl group the polymer backbone, both pEtEtOx and pPrMeOx series show less chain flexibility than pEtOx and pPrOx, respectively. Additionally, the results from TGA and DSC indicate that the thermal properties of p R EtEtOx, p S EtEtOx and p RS EtEtOx are similar, and that of p R PrMeOx, p S PrMeOx and p RS PrMeOx as well.