Geopolymer cement is an emerging eco-friendly alternative to traditional Portland cement that offers a lower carbon footprint and the opportunity to use of industrial by-products such as fly ash and slag in its production. Although acknowledged as a dependable structural material in various studies, the potential of Geopolymer Concrete for paving applications remains under-explored. This research aimed to address this gap by developing Paving Quality Geopolymer Concrete (PQGC) and examining its mechanical and thermal properties. For applications in tropical climates, where the pavement surface may be subjected to temperatures in the range 30–60 °C, studies on thermal conductivity (λ), coefficient of thermal expansion (α), and stresses caused by daily and seasonal temperature changes in PQGC slabs need to be essentially studied. The study revealed that thermal conductivity of PQGC ranged from λ = 0.82 W/(m°C) to 0.71 W/(m°C) within the temperature range of 30–60 °C. The coefficient of thermal expansion for PQGC was evaluated using a setup based on AASHTO T 336–15 recommendations, and it was found, α = 8 × 10–6/°C, to be lower than that of Pavement Quality Concrete (PQC). Furthermore, stresses resulting from temperature fluctuations in PQGC, when computed using closed form solution and EverFe 2.26, were observed to be lower than those in PQC. Finally, PQGC has the potential to contribute to a cooler environment by emitting less heat into its surroundings and promotes the utilisation of fly ash and slag, making it a promising material for paving applications.