The grain boundary diffusion process (GBDP) has proven to be an effective method for enhancing the coercivity of sintered Nd-Fe-B magnets. However, the limited diffusion depth and thicker shell structure have impeded the further development of magnetic properties. Currently, the primary debates regarding the mechanism of GBDP with Tb revolve around the dissolution-solidification mechanism and the atomic substitution mechanism. To clarify this mechanism, the microstructure evolution of sintered Nd-Fe-B magnets during the heating process of GBDP has been systematically studied by quenching at different temperatures. In this study, it was found that the formation of TbFe2 phase is related to the dissolution of Nd2Fe14B grains during GBDP with Tb. The theory of mixing heat and phase separation further confirms that the Nd2Fe14B phase dissolves to form a mixed phase of Nd and TbFe2, which then solidifies into the (Nd, Tb)2Fe14B phase. Based on the discovery of the TbFe2 phase, the dissolution-solidification mechanism is considered the primary mechanism for GBDP. This is supported by the elemental content of the two typical core-shell structures observed.