MoSe2 nanosheets with small size and expanded spaces between the (002) planes were grown on the surfaces of porous N-doped carbon nanotubes (NCNTs) with much higher HER activity than carbon nanotubes without N dopants. Owing to the synergistic effects between the MoSe2 nanosheets and the porous NCNT substrate, MoSe2/NCNTs exhibit superior HER activity to layered metal chalcogenides reported previously.