Electrospinning is a highly efficient mild method to obtain stereocomplex poly(lactic acid) fibers from blends of high molecular weight (MW) poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA). However, high MW PLAs are expensive and proved difficult to avoid homocrystallites which weaken the performances. Here, di-stereoblock poly(lactic acid)s (di-sb-PLAs) with low MW of 10(4) g mol(-1)were synthesized and electrospun into membranes. The stereocomplex (sc) crystallites were induced by sintering the amorphous as-spun membranes at 200 degrees C, and further improved by applying 1 MPa pressure which promoted the segment migration across fiber intersections and welded the fibers by forming new sc crystallites. Due to more readily crystallize at molecular level than the blend of PLLA and PDLA, the sintered di-sb-PLA membranes exhibited higher thermal stability, better tensile strength, and were more stable during multiple cycles of selective separating solvent and water mixtures. Increasing MW of di-sb-PLA positively affected the membrane properties and inhibited dramatical embrittlement that occurred in sintered membrane of PLLA and PDLA blend.