In this research, a new Thermal Insulating Concrete Block (TICB) is produced via “sandwich” structure by spent polystyrene foam, cement and other raw materials. According to the concerned China Standard Test Method for Building Material, the main properties of this TICB are measured successfully. By comparing its properties with those of autoclaved aerated concrete block as wall material, it can be concluded that comprehensive properties of this concrete block is better than those of autoclaved aerated concrete block. The extrusive advantage of producing this TICB is that large amount of spent polystyrene foam which is hard to be decomposed as industrial waste can be consumed. This is propitious to environmental protection and energy conservation. Therefore, TICB studied in this paper is one kind of green environmental wall material with bright prospect.