It has been suggested that mental habits may underpin a heightened disposition to engage in rumination in response to negative mood. The aim of the current study was to assess the role of habit in the dynamic interplay between affect and ruminative thinking in the flow of daily life experiences. Using mobile ecological momentary assessment, 97 participants recorded affect and rumination ten times daily over six days, after completing measures of trait ruminative brooding and habitual characteristics of negative thinking (e.g. automaticity, lack of conscious awareness, intent and control). Momentary fluctuations in negative (increased) and positive (decreased) affect was prospectively associated with greater rumination-levels at the next sampling occasion. The degree to which affect triggered a subsequent ruminative response was moderated by habitual characteristics of negative thinking in a theoretically consistent way. Stronger temporal pairing of negative affect and rumination was also associated with greater emotional inertia but less carry-over of rumination from one moment to the next. Depression vulnerability may be in the form of rumination being habitually triggered in response to momentary fluctuations in affect, with deleterious effect on mood. The findings may have clinical implications, as targeting the habitual nature of rumination might help reduce depression vulnerability.