In the present study, the performance of six popular density functionals (B3LYP, PBE0, BLYP, BP86, PBE, and SVWN) for the description of the autoionization process in the water octamer was studied. As a benchmark, MP2 energies with complete basis sets limit extrapolation and CCSD(T) correction were used. At this level, the autoionized structure lies 28.5 kcal(.)mol(-1) above the neutral water octamer. Accounting for zero-point energy lowers this value by 3.0 kcal(.)mol(-1). The transition state of the proton transfer reaction, lying only 0.7 kcal(.)mol(-1) above the energy of the ionized system, was identified at the MP2/aug-cc-pVDZ level of theory. Different density functionals describe the reactant and product with varying accuracy, while they all fail to characterize the transition state. We find improved results with hybrid functionals compared to the gradient-corrected ones. In particular, B3LYP describes the reaction energetics within 2.5 kcal(.)mol(-1) of the benchmark value. Therefore, this functional is suggested to be preferably used both for Carr-Parinello molecular dynamics and for quantum mechanics/ molecular mechanics (QM/MM) simulations of autoionization of water.