This work presents a 3D computational/mathematical model to solve the heat diffusion equation with phase change, considering metal addition, complex geometry, and thermal properties varying with temperature. The finite volume method was used and the computational code was implemented in C++, using a Borland compiler. Experimental tests considering workpieces of stainless steel AISI 304 were carried out for validation of the thermal model. Inverse techniques based on Golden Section method were used to estimate the heat transfer rate to the workpieces. Experimental temperatures were measured using thermocouples type J—in a total of 07 (seven)—all connected to the welded workpiece and the Agilent 34970A data logger. The workpieces were chamfered in a 45° V-groove in which liquid metal was added on only one weld pass. An innovation presented in this work when compared to other works in scientific literature was the geometry of the weld pool. The good relation between experimental and simulated data confirmed the quality and robustness of the thermal model proposed in this work.