Research suggests that transient emotional episodes produces sustained effects on psychological functions and brain activity during subsequent resting state. In this fMRI study we investigated whether transient emotions induced by smells could impact brain connectivity at rest in a valence-specific manner. The results suggest a sustained reconfiguration of parts of the default mode network which become more connected with areas implicated in olfactory processing, emotional learning, and action control. We found lingering effects of odorants on subsequent resting state that predominantly involved connections of the precuneus with a network comprising the insula, amygdala, medial orbital gyrus. Unpleasant smells in particular predicted greater coupling between insula, hippocampal structures, and prefrontal cortex, possible reflecting enhanced aversive learning and avoidance motivation. More broadly, our study illustrates a novel approach to characterize the impact of smells on brain function and differentiate the neural signatures of their valence, during task-free rest conditions.