Repeated sensory exposures shape the brain's function and its responses to environmental stimuli. An important clinical and scientific question is how exposure to pain affects brain network activity and whether that activity is modifiable with training. We sought to determine whether repeated pain exposure would impact brain network activity and whether these effects can be reversed by cognitive behavioral therapy (CBT)-based training. Healthy subjects underwent 8 experimental sessions on separate days on which they received painful thermal stimuli. They were randomly assigned to groups receiving either CBT-based training (regulate group, n = 17) or a non-pain-focused treatment (control group, n = 13). Before and after these sessions, participants underwent functional magnetic resonance imaging (fMRI) during painful stimulation and at rest. The effect of repeated pain over time in the control group was a decrease in the neurotypical pain-evoked default mode network (DMN) deactivation. The regulate group did not show these DMN effects but rather had decreased deactivation of the right ventrolateral prefrontal cortex (R vlPFC) of the executive control network. In the regulate group, reduced pain-evoked DMN deactivation was associated with greater individual reduction in pain intensity and unpleasantness over time. Finally, the regulate group showed enhanced resting functional connectivity between areas of the DMN and executive control network over time, compared with the control group. Our study demonstrates that trainable cognitive states can alter the effect of repeated sensory exposure on the brain. The findings point to the potential utility of cognitive training to prevent changes in brain network connectivity that occur with repeated experience of pain.