In order to explore the thermal characteristics and thermal storage performance analysis of energy-saving phase change heat storage materials in buildings, taking the common exterior wall insulation composite wall structure in southwestern China as an example, the influence of insulation board structure thickness design on the total cost of residential air conditioning energy consumption and insulation board cost is studied, thus clarifying the concept and calculation origin of economic insulation thickness. The experimental results show that by drawing mathematical functions of energy consumption cost, total cost, and insulation material cost in the same 2-D coordinate, it is intuitively demonstrated that the minimization of total cost can be ensured when the insulation thickness is in an economic state, and the specific economic thickness can be accurately calculated through example data. Therefore, specific measures for improving external wall insulation from refined insulation structure design are proposed. It has been proven that the design of the exterior wall insulation layer structure is an important way to improve the overall energy-saving benefits of building exterior wall insulation.