The Volume-of-Fluid (VOF) method is commonly used for numerical simulations of phase change phenomena, such as nucleate boiling or droplet evaporation. A key issue with the standard VOF method is the averaging of the liquid and vapor properties in interface cells, which causes non-physical conjugate heat transfer with a solid wall. Therefore, we aim at a physical model for conjugate heat transfer between a solid and a multiphase fluid. The first measure for higher quality simulations is the splitting of the single temperature field in the fluid region into separate liquid and vapor temperature fields. The second measure is the development of a new, more physical temperature boundary condition for conjugate heat transfer between a solid region and a multiphase fluid, based on experimental results, theoretical models and theoretical considerations. In interface cells, the vapor phase is excluded from the conjugate heat transfer because only heat transfer to the liquid phase occurs resp. dominates. Additionally, the conjugate heat transfer between solid and liquid in the interface cells is performed with virtual subcells, depending on the respective volume fraction of the liquid phase. This new approach (we name it distinctive approach) is successfully validated for energy conservation, and stability issues are discussed for the first time. Significant differences to simulations with averaged properties are observed due to the (now) physically correct modeling of conjugate heat transfer. In our boiling cases, the more accurate numerical simulations lead to considerably larger bubble growth rates. Higher quality simulations are also expected for nearly all applications, where there is a three-phase contact line, be it vapor bubbles in nucleate boiling or droplets impacting on a heated surface.