The film thickness of asphalt mixtures is critical for determining their performance and aging durability. However, understanding of the appropriate film thickness and its influence on performance and aging behavior for high-content polymer-modified asphalt (HCPMA) mixtures is still limited. This research aims to examine the relationship between film thickness, performance, and aging behavior of HCPMA mixtures in order to establish an optimal film thickness that ensures satisfactory performance and aging durability. HCPMA specimens with film thicknesses ranging from 6.9 μm to 17 μm were prepared using a 7.5% SBS-content-modified bitumen. Various tests, including Cantabro, SCB, SCB fatigue, and Hamburg wheel-tracking tests, were conducted to evaluate raveling, cracking, fatigue, and rutting resistance before and after aging. The key findings indicate that insufficient film thickness negatively affects aggregate bonding and performance, while excessive thickness reduces mixture stiffness and resistance to cracking and fatigue. A parabolic relationship between the aging index and film thickness was observed, suggesting that increasing film thickness improves aging durability up to a point, beyond which excessive thickness adversely impacts aging durability. The optimal film thickness for HCPMA mixtures, considering performance before and after aging and aging durability, falls within the 12.9 to 14.9 µm range. This range ensures the best balance between performance and aging durability, offering valuable insights for the pavement industry in designing and utilizing HCPMA mixtures.