Sustainability and the quest for a more robust construction material cannot be divorced from each other. While Portland cement has revolutionized the construction sector, its environmental toll, particularly in greenhouse gas emissions and global warming, cannot be ignored. Addressing this dilemma requires embracing alternatives like geopolymer cement/geopolymer binder (GPC/GPB). Over the last few decades, considerable strides have been achieved in advancing GPC as a sustainable construction material, including its utilization in pavement construction. Despite these advances, gaps still exist in GPC optimal potential in pavement construction, as most studies have concentrated on specific attributes rather than on a comprehensive evaluation. To bridge this gap, this review adopts a novel, holistic approach by integrating environmental impacts with performance metrics. To set the stage, this review first delves into the geopolymer concept from a chemistry perspective, providing an essential broad overview for exploring GPC’s innovations and implications in pavement applications. The findings reveal that GPC not only significantly reduces greenhouse gas emissions and energy consumption compared to Portland cement but also enhances pavement performance. Further, GPC concrete pavement exhibits superior mechanical, durability, and thermal properties to ensure its long-term performance in pavement applications. However, challenges to GPC utilization as a pavement material include the variability of raw materials, the need for suitable hardeners, the lack of standardized codes and procedures, cost competitiveness, and limited field data. Despite these challenges, the process of geopolymerization presents GPC as a sustainable material for pavement construction, aligning with Sustainable Development Goals (SDGs) 3, 9, 11, and 12.