The effect of H2plasma exposure on CuInSe2was studied by synchrotron radiation soft‐x‐ray photoemission spectroscopy. The low‐power H2plasma was generated with a commercial electron cyclotron resonance plasma source using pure H2with the plasma exposure being performed at 200 °C.Insituphotoemission measurements were acquired after each plasma exposure in order to observe changes in the valence‐band electronic structure as well as changes in the In 4dand Se 3dcore lines. The results were correlated in order to relate changes in surface chemistry to the electronic structure. These measurements indicate that the H2plasma exposure type converts the CuInSe2surface to ann‐type surface as well as converting the In+3valency state to an In+1valency state.