The doping effect of rare earth elements (Tb and Sm) on the electronic structure of (110) martensitic twin boundary in Ni2MnGa alloys was investigated by using ab initio method within the DFT and the supercell implementation. The calculated results show that the atomic relaxation lowers the boundary energy and the segregation energy. Sm seems easier to segregate to the boundary and has a greater doping effect compared with Tb due to its lower segregation energy and bigger bonder order with neighboring atoms. Tb makes a greater contribution to the magnetic properties of the twin boundary than Sm.