Smoking and stress cooccur in different stages of a nicotine addiction cycle, affecting brain function and showing additive impact on different physiological responses. Resting-state functional connectivity has shown potential in identifying these alterations. Nicotine addiction has been associated with detrimental effects on functional integrity of the central nervous system, including the organization of resting-state networks. Prolonged stress may result in enhanced activation of the default mode network (DMN). Considering that biofeedback has shown promise in alleviating physiological manifestations of stress, we aimed to explore the possible neuroplastic effects of biofeedback training on smokers. Clinical, behavioral, and neurophysiological (resting-state EEG) data were collected from twenty-seven subjects before and after five sessions of skin temperature training. DMN functional cortical connectivity was investigated. While clinical status remained unaltered, the degree of nicotine dependence and psychiatric symptoms were significantly improved. Significant changes in DMN organization and network properties were not observed, except for a significant increase of information flow from the right ventrolateral prefrontal cortex and right temporal pole cortex towards other DMN components. Biofeedback aiming at stress alleviation in smokers could play a protective role against maladaptive plasticity of connectivity. Multiple sessions, individualized interventions and more suitable methods to promote brain plasticity, such as neurofeedback training, should be considered.