In this study, organocatalytic systems containing both basic and acidic sites, which can activate simultaneously the chain end and the monomer, were investigated in the ring-opening polymerization of L-lactide. To this end, equivalent amounts of (N,N-dimethylamino)pyridine (DMAP) and of its protonated form (DMAP center dot HX) were used as a dual catalytic system for L-lactide polymerization initiated by different alcohols. It is shown that the corresponding DMAP/DMAP center dot HX systems are significantly more active than DMAP alone, and yield well-controlled poly(L-lactide). Depending on the reaction conditions, the transesterification reaction can be prevented.