High-resolution angle-integrated photoemission of one monolayer of C (60) chemisorbed on Ag(100) shows the reversible opening of a gap at the Fermi level at temperatures 25< or =T< or =300 K. The gap reaches a maximum value of approximately 10 meV at T< or =70 K. This finding is the first evidence of an electronic phase transition in C60 monolayers and has implications on the ongoing debate about surface superconductivity in C60-based bulk materials.