In this paper, we proposed a procedure for calculation of room temperature in multi-room building using the backward-difference method. Based on this procedure and using our simulation program, we evaluated CO2 reduction by installating high light-reflective and high heat-emissive paint in buildings. Heat balance equations on each heat point in each room or wall in the building were deduced from one-dimensional heat-conduction equation and converted to the matrix equation. We improved matrix computing and developed a different procedure from conventional methods. Because this procedure is simple, we consider that this is applicable to estimation of most building’s technologies. As its application, the effects of high light-reflective and high heat-emissive paint was evaluated. Although the paint increases heating load, it can reduce cooling load. We thus conclude that the paint is effective for CO2 reduction.