Poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) alternatively pack with each other and form stereocomplex crystals (SCs). The crystal habits of SCs formed in the dilute solution highly depend on the molecular weight (⟨Mw⟩). In this study, we investigated chain-folding (CF) structure for 13C labeled PLLA (l-PLLA) chains in SCs with PDLAs that have either high or low ⟨Mw⟩s by employing an advanced Double Quantum (DQ) NMR. It was found that the ensemble average of the successive adjacent re-entry number ⟨n⟩ for the l-PLLA chains drastically change depending on ⟨Mw⟩s of the counter PDLA chains in the SCs. It was concluded that the CF structures of l-PLLA depending on ⟨Mw⟩s of PDLA determine the crystal habits of SCs.