The temperature dependence of the rate of the reaction of OH with 2‐(dimethylamino)‐ethanol, (CH₃)₂NCH₂CH₂OH (DMAE) was investigated over the temperature range, 234 to 364 K. The reaction was studied using the flash photolysis‐resonance fluorescence technique. The room temperature rate constant determined for this reaction was (10.3 ± 2.0) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, with essentially no temperature dependence evident within the uncertainty in the experiments. A value of (9.0 ± 2.0) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ is believed to best describe the reaction over the entire temperature range. The room temperature rate constant is about twice the value reported previously for this reaction. The overall reaction of OH with DMAE was apportioned to the reactivity of OH for abstracting individual H‐ atoms from different types of CH bonds and the OH bond within the molecule. This technique predicts the overall rate constant for the OH‐DMAE reaction to within about 15% of the experimental value and makes it possible to estimate the yields of the initial radical products of the OH attack on DMAE. A mechanism is proposed for the subsequent atmospheric reactions that would occur in the photooxidation of DMAE.