Applying a large amount of fly ash to foam concrete can greatly reduce the engineering cost, but the proportion of fly ash is limited due to insufficient pozzolanic activity and heavy metal pollution. Therefore, this study used fly ash, portland cement, fly ash ceramsite, foaming agent, etc. as raw materials to design the mix ratio of large-volume fly ash foam concrete. The micro-interface enhancement mechanism was deeply analyzed, and a multi-method pollution assessment system was finally established for the risk assessment of heavy metals. The dry bulk density of the fly ash foam concrete prepared in this study was 894.5 kg/m3, the compressive strength was 4.22 MPa, and the thermal conductivity is 0.2213 W/(m K). These parameters all met the requirements of the Chinese standard “Foam Concrete” (JG/T 266-2011). The microscopic analysis results showed that, compared with the fly ash content of 60%, the foam concrete with 40% fly ash content had more rodlike ettringite at the interface of the pore wall, and its hydration products were distributed more uniformly. Similarly, the interface between the ceramsite mixed with 40% fly ash and the cement stone was more closely combined, the distribution of hydration products between the interfaces was more uniform, and the interface quality was higher. After adding thickener, the pore distribution of fly ash foam concrete was tight, and there were a lot of small pores between the pores, and the pore structure had better connectivity than when no thickener was added. The evaluation results of foamed concrete with 40% fly ash content with the aid of the multi-method pollution assessment system showed that the harmful heavy metals in fly ash were stably solidified in the silicate structure, resulting in low leaching efficiency. Finally, the performance of the high-volume fly ash foamed concrete slab produced according to the mix ratio designed in this study met the requirements of “Light weight panels for partition wall used in buildings” (GB/T 23,451-2009). Therefore, it is a safe and environmentally friendly high-performance building product.