Background: Sub-Saharan Africa (SSA) faces a dual challenge of limited access to essential opioids for pain relief and increasing concerns about misuse, diversion, and trafficking. Despite opioids being classified as essential medicines, access across the region remains constrained by restrictive laws, fragmented governance, limited provider training, and widespread stigma. While calls for more balanced opioid policies exist, systematic evidence on access and governance in SSA remains limited. This systematic review synthesises existing data to inform policy, practice, and research. Methods: The review was reported according to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. A comprehensive search of six electronic databases and relevant grey literature was conducted. Studies were included if they focused on any SSA country and examined opioid policy, access, regulation, or governance. Only English-language studies published between 1990 and 2024 were included. Two reviewers independently screened and assessed study quality. Thematic and content analysis were used for data synthesis. Results: Thirty-three studies met inclusion criteria, covering diverse SSA contexts. Five major themes were identified: policy and regulatory frameworks, barriers to access, governance and institutional roles, political influences, and data gaps. Across most settings, restrictive regulations, operational bottlenecks, weak health systems, stigma, and insufficient training impede opioid availability. Policies often emphasise control over care, contributing to widespread untreated pain. While some countries have implemented reforms and harm reduction strategies, coordination and surveillance remain limited. Conclusions: Expanding opioid access in SSA requires regulatory reform, decentralised prescribing, provider training, and investment in harm reduction and health infrastructure. A balanced, rights-based approach is needed to address both the undertreatment of pain and the risks of misuse. However, this review is limited by its reliance on studies published in English, resulting in a geographically skewed evidence base. This highlights the urgent need for more inclusive and representative research across diverse Sub-Saharan African contexts. Protocol Registration: The protocol was prospectively registered with PROSPERO (CRD42025637149).