Neuroimaging studies have revealed the recruitment of a range of neural networks during the resting state, which might reflect a variety of cognitive experiences and processes occurring in an individual's mind. In this study, we focused on the default mode network (DMN) and attentional networks and investigated their association with distinct mental states when participants are not performing an explicit task. To investigate the range of possible cognitive experiences more directly, this study proposes a novel method of resting-state fMRI experience sampling, informed by a phenomenological investigation of the fluctuation of mental states during the resting state. We hypothesized that DMN activity would increase as a function of internal mentation and that the activity of dorsal and ventral networks would indicate states of top–down versus bottom–up attention at rest. Results showed that dorsal attention network activity fluctuated as a function of subjective reports of attentional control, providing evidence that activity of this network reflects the perceived recruitment of controlled attentional processes during spontaneous cognition. Activity of the DMN increased when participants reported to be in a subjective state of internal mentation, but not when they reported to be in a state of perception. This study provides direct evidence for a link between fluctuations of resting-state neural activity and fluctuations in specific cognitive processes.