This paper presents a study of the hot plate method with two simultaneous temperature measurements, on the heated and unheated faces of a sample to characterize. The thermal properties of polyvinyl chloride, plaster and laterite were considered to be a representative range of building materials. A 1D quadrupolar model was developed to represent the temperature evolution on the two faces over time. Three-dimensional numerical modeling of a quarter of the testing device with COMSOL software allowed defining the domain of the 1D hypothesis validity. The analysis of estimation possibilities of materials’ thermal characteristics, with the developed method, revealed that thermal effusivity can be accurately estimated by using the temperature of the heated face at the beginning of heating. We showed that the simultaneous use of two temperatures enables the estimation of the thermal conductivity with a greater accuracy and over a shorter time interval than using the temperature of the heated face alone. We also demonstrated that under certain conditions (samples with a high ratio of thickness to width) the method with two temperature measurements enabled the estimation of the thermal effusivity and conductivity, while the method with one temperature allowed only the thermal effusivity to be estimated, because of 3D effects. This conclusion was confirmed by experimental results obtained with a mortar sample.