Nowadays, mindfulness-based interventions (MBI) have experienced a remarkable development of studies among childhood and adolescent interventions. For this reason, dispositional mindfulness (DM) measures for children and adolescents have been developed to determine the effectiveness of MBI at this age stage. However, little is known about how key elements of DM (for example, cognitive de/fusion or experiential avoidance that both confirm psychological inflexibility) are involved in the mechanisms of the children and adolescents’ mental health outcomes. This research examined the mediating effect of cognitive fusion between DM and anxiety and other negative emotional states in a sample of 318 Spanish primary-school students (aged between 8 and 16 years, M = 11.24, SD = 2.19, 50.8% males). Participants completed the AFQ-Y (Avoidance and Fusion Questionnaire for youth), which is a measure of psychological inflexibility that encompasses cognitive defusion and experiential avoidance; CAMM (DM for children and adolescents), PANAS-N (positive and negative affect measure for children, Spanish version of PANASC), and STAIC (an anxiety measure for children). The study accomplished ethical standards. As MBI relevant literature has suggested, cognitive defusion was a significant mediator between DM and symptoms of both negative emotions and anxiety in children and adolescents. However, experiential avoidance did not show any significant mediating relationship. Probably, an improvement of the assessment of experiential avoidance is needed. MBI programs for children and adolescents may include more activities for reducing effects of the cognitive defusion on their emotional distress.