Control of stereoregularity is inherent to precision polymerization chemistry for the development of functional materials. A prototypal example of this strategy is the ring-opening polymerization (ROP) of racemic lactide (rac-LA), a bio-sourced monomer. Despite significant advances in organocatalysis, stereoselective ROP of rac-LA employing chiral organocatalysts remains unexplored. Here we tackle that challenge by resorting to Takemoto's catalyst, a chiral aminothiourea, in the presence of a phosphazene base. This chiral binary organocatalytic system allows for fast, chemo- and stereoselective ROP of rac-LA at room temperature, yielding highly isotactic, semi-crystalline and metal-free polylactide, with a melting temperature as high as 187 °C.