The urban heat island effect raises road surface temperatures, increasing energy demands and accelerating pavement deterioration. This study evaluates a polymer-based pavement system using methyl methacrylate (MMA) resin with aluminum silicate (AS), glass bubbles (GBs), and microencapsulated n-docosane phase-change material (PCM) to identify the most effective solution. Indoor laboratory tests determined AS as the optimal choice, balancing thermal insulation, workability, and mechanical strength. AS-containing mixtures reduced surface temperatures by ~10 °C and exhibited superior compressive strength (28.2 MPa at 6 wt%) compared to GB (23.7 MPa at 4 wt%) and PCM (27.2 MPa at 6 wt%). AS also maintained stable viscosity at ≤10 wt%, unlike GB and PCM, which became unworkable above 5 wt%. The AS-based system achieved high skid resistance (90.2 BPN), abrasion resistance (0.1% wear after 500,000 cycles), and low VOC emissions (69.64 g/L). Adjusting the resin-to-BPO ratio to 1:0.42 enabled a 30 min curing time at 25 °C, ensuring practical application. These findings highlight AS as the most effective filler for large-scale deployment. Future work should assess long-term durability and optimize formulations for broader adoption in heat-mitigating infrastructure.