C-60:Li@C-60 hybrid n-type semiconducting films were first fabricated. The Fermi level of 1\% Li@C-60-added C-60 films was determined to be -4.52 eV, which was 0.12 eV higher than that of pristine C-60 films. A fraction of Li@C-60 is distributed uniformly within the C-60 film. Its application in PSCs was demonstrated, in which the addition of Li@C-60 into a C-60 film improved the device performance.