Design of the polymer networks with tunable mechanical properties and multishape memory effects (multi- SMEs) is highly desired in the engineering applications. Herein, we report on the stereocomplexed and homochiral polyurethane (PU) elastomers with tunable multi-SMEs by cross-linking the triblock prepolymers bearing the poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA) enantiomeric segments. The homochiral PU is nearly amorphous, yet the stereocomplexed PU becomes highly crystalline due to the stereocomplexation of enantiomeric segments. Moreover, the two distinct thermal (glass, melting) transitions of PLLA (or PDLA) segments in PUs are integrated to realize the thermally induced triple- and quadruple- SMEs. Control over the enantiomeric segmental ratios allows the feasible manipulation of crystallizability, mechanical and thermal properties, and multi-SMEs of PUs.