The soil–water characteristic curve (SWCC) plays an important role in solving the stability and deformation problems of unsaturated soils. In many practical situations, soils are usually experienced by both deformations and thermal conditions. In this interest, the paper proposes a simple and effective model to predict the combined effect of initial density and temperature on the SWCC and to be able to quantify the changes in thermal-hydro-mechanical behavior of unsaturated soils. In the first step, an initial density-dependent SWCC model is presented using the translation principle between particle-size distribution curve and soil–water characteristic curve. In the second part, a non-isothermal model is proposed to predict the effect of temperature on the SWCC. The key to the non-isothermal model is considering five different temperature-dependent functions, which are surface tension, contact angle, particle-size expansion, void ratio, and water density. On the basis of 22 data sets of thermal volume change, this study also developed further a theoretical correlation between void ratio and temperature that is directly related to soil plasticity. It was observed that the value of the thermal void ratio increases as soil plasticity increases, and there is a nonlinear relationship between the plasticity index and the void ratio. Because of this, soils with high plasticity are more susceptible to volume changes caused by temperature fluctuations than soils with low plasticity. A coupled mechanical–thermal model is then produced which is capable to predict separately or simultaneously the effect of temperature and initial density on SWCC. The proposed model is validated against several test data sets available in the literature. The results show that the proposed model has a good performance in predicting the variation in SWCC with arbitrary temperature and initial density.