The charge recombination dynamics of the ion pairs formed upon electron-transfer quenching of perylene by tetracyanoethylene in acetonitrile has been investigated using ultrafast fluorescence upconversion, transient absorption, and transient grating techniques. For this donor/acceptor pair, charge separation is highly exergonic (ΔG[CS]= −2.2 eV), but charge recombination is weakly exergonic (ΔG[CR] = −0.6 eV). It was found that for more than 90% of the ion pair population, charge recombination is ultrafast and occurs in less than 10 ps. This decay component could not be observed in a previous investigation with a lower time resolution. The results indicate that the primary quenching product is a contact ion pair and not a solvent-separated ion pair as generally assumed for highly exergonic electron-transfer quenching processes. A possible explanation for this apparent divergence is that the contact ion pair is initially formed in an electronic excited state. Only a very minor fraction of the ion pair population undergoes the slow charge recombination predicted by Marcus theory for weakly exergonic charge-transfer processes (normal region).