Silyl‐terminated oligomers of poly(l‐lactide) (mSi‐PLLA) and poly(d‐lactide) (mSi‐PDLA) were synthesized by hydrosilylation of allyl‐terminated derivatives. They were readily hydrolyzed into hyper‐branched polymers having particulate morphology. When a mSi‐PDLA oligomer was blended with a PLLA sample (52.5 kDa) in 1–10 wt.‐% by solution casting, small cross‐linked particles with stereocomplex form were generated and distributed homogenously in the PLLA matrix, and by which the homo‐chiral crystallization of PLLA was efficiently suppressed. When another mSi‐PLLA oligomer was blended with PLLA, the cross‐linked particles formed from mSi‐PLLA were amorphous and distributed inhomogeneously. It was, therefore, indicated that the hydrolytic polycondensation of mSi‐PDLA and mSi‐PLLA was induced during the film casting, changing the inner structure and properties of the blend films with PLLA.