This work compares the electrochemical windows of polished and unpolished boron doped diamond (BDD) electrodes with hydrogen and oxygen terminations at a series of temperatures up to 125 °C. The experiment was run at 5 bar pressure to avoid complications due to bubble formation. An alternative method for determining the electrochemical window is compared to the most commonly used method, which defines the window at an arbitrary current density cut-off (Jcut-off) value. This arbitrary method is heavily influenced by the mass transport of the electrolyte and cannot be used to compare electrodes across literature where different Jcut-off values have been used. A linear fit method is described which is less affected by the experimental conditions in a given measurement system. This enables a more accurate comparison of the relative electrochemical window from various diamond electrode types from reported results. Through comparison of polished and unpolished BDD electrodes, with hydrogen and oxygen surface terminations, it is determined that the electrochemical window of BDD electrodes narrows as temperature increases; activation energies are reported.