People’s minds frequently wander towards self-generated thoughts, which are unrelated to external stimuli or demands. These phenomena, referred to as “spontaneous thought” (ST) and “mind wandering” (MW), have previously been linked with both costs and benefits. Current assessments of ST and MW have predominantly been conducted in the laboratory, whereas studies on the ecological validity of such lab-related constructs and their interrelations are rare. The current study examined the stability of ST dimensions assessed in the lab and their predictive value with respect to MW, repetitive negative thought (uncontrollable rumination, RUM), and affect in daily life. Forty-three university students were assessed with the Amsterdam Resting State Questionnaire (2nd version) to assess ten ST dimensions during the resting state in two laboratory sessions, which were separated by five days of electronic ambulatory assessment (AA). During AA, individuals indicated the intensity of MW and RUM, as well as of positive and negative affect in daily life ten times a day. ST dimensions measured in the lab were moderately stable across one week. Five out of ten ST lab dimensions were predicted by mental health-related symptoms or by dispositional cognitive traits. Hierarchical linear models revealed that a number of ST lab dimensions predicted cognitive and affective states in daily life. Mediation analyses showed that RUM, but not MW per se, accounted for the relationship between specific ST lab dimensions and mood in daily life. By using a simple resting state task, we could demonstrate that a number of lab dimensions of spontaneous thought are moderately stable, are predicted by mental health symptoms and cognitive traits, and show plausible associations with categories of self-generated thought and mood in daily life.