We have examined the titled reaction near its threshold using the pulsed field ionization photoelectron–photoion coincidence method. The measured 0 K threshold (18.220±0.002 eV) has made possible the determination of more precise values for the 0 K bond dissociation energies for D–OD+ (5.584±0.002 eV) and D–OD (5.191±0.002 eV) and the 0 K heats of formation (ΔH0f0's) for OD+ (308.83±0.05 kcal/mol) and OD (8.38±0.05 kcal/mol). We found that the available energetic data for the OD/OD+ and D2O/D2O+ system are in excellent agreement with those for the OH/OH+ and H2O/H2O+ system after taking into account the zero-point vibration energies of these species.