The energy use of building systems contributes to a large percentage of total energy consumption, which requires consideration. Solutions of improvement to save energy are crucial. Phase change materials have been proved to be good candidates to be used in building envelopes for energy save. In this paper, an extended Explicit Finite Element Method (ex-FEM), which has been previously introduced and improved, is taken for simulation of temperatures and heat transfer in simplified multilayer wall constructions, consisting of PCM and insulation. The method has been validated against experimental data measured in a so-called Hot-Box. Temperature data are measured at different positions in a number of simplified multilayer walls. Our results show a reasonable good agreement between the simulations and the experiments, at both heating and cooling considering the temperature hysteresis effect in the PCM. The temperature stabilization ability of the PCM is clear, in both the simulations and the experiments, and particularly in the data when the transition range of the PCM is fully activated and matching the temperature variation in the wall at that particular PCM position. Our ex-FEM tool has here been proved to be able to predict the thermal performance of simplified wall constructions of multiple layers with PCMs incorporated.