There are a myriad of obstacles faced by individuals who take medication for opioid use disorder, including high out-of-pocket costs, stigma, logistical challenges associated with traveling to treatment facilities, and negative experiences with treatment providers. The proliferation of illicit fentanyl use and associated overdose risk underscores the urgent need to broaden access to lifesaving pharmacotherapy for opioid use disorder. This case report describes the safe and effective induction of a 32-year-old male onto sublingual buprenorphine in a digital care setting, with integrated, counselor-facilitated psychosocial treatment delivered via a smartphone app targeting relapse prevention. The digital care modality enabled this patient to overcome 2 major treatment barriers: limited access to evidence-based treatment given his residence in a rural area, and heightened overdose risk given his use of fentanyl, a potent synthetic opioid. In addition, we describe tobacco cessation treatment delivered digitally concurrently with opioid use disorder care, combining pharmacotherapy and behavioral skills training. Given the disproportionately high rate of co-occurring opioid use disorder and tobacco use and associated mortality rates, the effective treatment of these conditions simultaneously in this case advances our knowledge of potentially efficacious treatment approaches for underserved individuals with opioid use disorder who present with polysubstance use.