The ultrafast charge separation at the quantum dot (QD)/molecular acceptor interface was investigated in terms of acceptor concentration and the size of the QD. Time-resolved experiments revealed that the electron transfer (ET) from the photoexcited QD to the molecular acceptor methylviologen (MV(2+)) occurs on the fs time scale for large acceptor concentrations and that the ET rate is strongly reduced for low concentrations. The increase in the acceptor concentration is accompanied with a growth in the overlap of donor and acceptor wavefunctions, resulting in a faster reaction until the MV(2+) concentration reaches a saturation limit of 0.3-0.4 MV(2+) nm(-2). Moreover, we found significant QD size dependence of the ET reaction, which is explained by a change of the free energy (ΔG).