Diffusion behavior of Nb in elemental powder metallurgy high Nb containing TiAl alloys was investigated. The results show that Nb element dissolves into the matrix by diffusion. Pore nests are formed in situ after Nb diffusion. With the increase in hot pressing temperature, the diffusion of Nb will be more sufficient, and the microstructure is more homogeneous. Nb element diffuses completely at 1400℃. Meanwhile, compression deformation and agglomeration phenomena of pores are observed in some pore nests. Hot isostatic pressing (HIP) treatment can only efficiently decrease but not eliminate porosity completely.