In response to the contemporary demands of the construction industry for climate-change action and carbon neutrality, this study conducts a comprehensive analysis of the applicability of Portland limestone cement (PLC)—a notable sustainable alternative to ordinary Portland cement (OPC)—for highway pavement applications. PLC is an eco-friendly material that reduces carbon-dioxide emissions and energy consumption compared with OPC by reducing the clinker ratio in its manufacturing process. This study examines the fundamental physical and chemical mechanisms of PLC concrete and compares its mechanical performance and durability characteristics with those of OPC concrete. The results indicate that PLC concrete exhibits performance levels equivalent to or superior to those of OPC in key metrics such as compressive and flexural strengths, with particularly outstanding performance in durability aspects such as chloride-penetration resistance. However, the potential for early-age cracking and compatibility issues with certain admixtures are identified as challenges that must be addressed for the wider field application of PLC concrete. Thus, this study proposes the integration of nanotechnology to overcome these technical limitations and maximize performance. Specifically, methods to significantly improve the strength, abrasion resistance, fatigue resistance, and crack-control performance by utilizing nanomaterials such as Nano- , Nano- , and graphene oxide ( ) to control the microstructure of PLC concrete are presented. Finally, a comprehensive roadmap is proposed to enhance the field applicability of PLC concrete for highway pavements and contribute to the construction of sustainable social infrastructure through three key strategies: mix design optimization, consideration of regional environmental conditions, and integration of nanotechnology.