Carbon coating is a simple, effective and common technique for improving the conductivity of active materials in lithium ion batteries. However, carbon coating provides a strong reducing atmosphere and many factors remain unclear concerning the interface nature and underlying interaction mechanism that occurs between carbon and the active materials. Here, we present a size-dependent surface phase change occurring in lithium iron phosphate during the carbon coating process. Intriguingly, nanoscale particles exhibit an extremely high stability during the carbon coating process, whereas microscale particles display a direct visualization of surface phase changes occurring at the interface at elevated temperatures. Our findings provide a comprehensive understanding of the effect of particle size during carbon coating and the interface interaction that occurs on carbon-coated battery material--allowing for further improvement in materials synthesis and manufacturing processes for advanced battery materials.