Cement-based building materials are fundamental for constructing modern buildings, and accurate determination of their thermal conductivity is crucial for calculating building energy consumption. In this study, random growth theory is used to reconstruct the two-dimensional pore structures of cement-based building materials in different forms. Furthermore, heat transfer simulations and calculations of effective thermal conductivity based on the finite element method are conducted for these pore structures. The effect of pore structure parameters on the effective thermal conductivity of cement-based building materials is investigated by this method. The results indicate that porosity, pore size, and the degree of pore regularity can all influence the effective thermal conductivity of cement-based building materials. At a porosity of 0.3, the fluctuations in the effective thermal conductivity caused by variations in pore sizes and degrees of pore regularity are most drastic.