Affect monitoring is being discussed as a novel strategy to make adaptive systems more user-oriented. Basic knowledge about oscillatory processes and functional connectivity underlying affect during naturalistic human–computer interactions (HCI) is, however, scarce. This study assessed local oscillatory power entrainment and distributed functional connectivity in a close-to-naturalistic HCI-paradigm. Sixteen participants interacted with a simulated assistance system which deliberately evoked positive (supporting goal-achievement) and negative (impeding goal-achievement) affective reactions. Electroencephalography (EEG) was used to examine the reactivity of the cortical system during the interaction by studying both event-related (de-)synchronization (ERD/ERS) and event-related functional coupling of cortical networks towards system-initiated assistance. Significantly higher α-band and β-band ERD in centro-parietal and parieto-occipital regions and β-band ERD in bi-lateral fronto-central regions were observed during impeding system behavior. Supportive system behavior activated significantly higher γ-band ERS in bi-hemispheric parietal-occipital regions. This was accompanied by functional coupling of remote β-band and γ-band activity in the medial frontal, left fronto-central and parietal regions, respectively. Our findings identify oscillatory signatures of positive and negative affective processes as reactions to system-initiated assistance. The findings contribute to the development of EEG-based neuroadaptive assistance loops by suggesting a non-obtrusive method for monitoring affect in HCI.