(1) Background: Internet gaming disorder (IGD) in youths likely leads to disruptive mood dysregulation, especially among those with attention-deficit/hyperactivity disorder (ADHD). Whether IGD mediates the pathways leading ADHD to disruptive emotional dysfunction remains unclear. This study aims to elucidate the direct or indirect influence of IGD on ADHD; (2) Method: The Swanson, Nolan, and Pelham Version IV questionnaire was used to evaluate symptoms of ADHD and oppositional defiant disorder, and the Chen gaming disorder scale was used to measure IGD. A psychiatrist diagnosed ADHD, IGD, and disruptive mood dysregulation disorder (DMDD)-like symptoms. Structural equation modeling was applied to evaluate the role of IGD in mediating ADHD progression to disruptive mood dysregulation; (3) Results: Among a total of 102 ADHD youths, 53 (52%) of them with IGD were significantly more likely to have poor interpersonal relationships (p < 0.01) and DMDD-like symptoms (p < 0.01) than ADHD youths without IGD. IGD played a mediating role in increasing the risk of disruptive mood dysregulation in ADHD youths; (4) Conclusions: The findings suggest that IGD mediates ADHD’s progression to disruptive mood dysregulation. Intensive biopsychosocial interventions are warranted for ADHD youths with IGD. More children and adolescents became mood-dysregulated after excessive gaming during the COVID-19 pandemic; this study’s results suggest that child mental health experts develop earlier detection and prevention strategies for children and adolescents hidden behind internet addiction.