Polylactide (PLA), the popular bio-based plastics, has attracted more interest as a benign alternative for oil-based plastics. Lowering the manufacture cost of PLA and improving the performance of PLA products are the essential challenges in PLA study. PLA stereocomplex is a promising choice to improve the thermal and mechanical properties. Efficient preparation of the PLA stereocomplex by the direct ring-opening polymerization (ROP) of inexpensive racemic lactide (roc-LA) requires the ROP catalysts with high activity and stereoselectivity. For this purpose, the novel trinuclear Salen-aluminum complexes were prepared in this work and exerted extraordinary improvement of catalytic activity and stereoselectivity at the same time. These complexes showed the excellent isoselectivity (typically P-m = 0.98), high activity (typically k(p) = 15.4 L mol(-1) min(-1)), and low catalyst loading amount (0.01 mol %). The T-m of PLA was 219.9 degrees C, which is the highest value among the reported PLA derived directly from rac-LA until now. It may foreshadow a new vista in the reduction of overall production cost and performance improvement of PLA to be competitive with oil-based commodity or engineering plastics.