We present observations of thermal (~0.6--100eV) electrons observed near Saturn's main rings during Cassini's Saturn Orbit Insertion (SOI) on 1 July 2004. We find that the intensity of electrons is broadly anticorrelated with the ring optical depth at the magnetic footprint of the field line joining the spacecraft to the rings. We see enhancements corresponding to the Cassini division and Encke gap. We suggest that some of the electrons are generated by photoemission from ring particle surfaces on the illuminated side of the rings, the far side from the spacecraft. Structure in the energy spectrum over the Cassini division and A-ring may be related to photoelectron emission followed by acceleration, or, more likely, due to photoelectron production in the ring atmosphere or ionosphere.