Vibrational sum frequency generation (VSFG) spectroscopy was used to measure the interfacial spectra of fullerene thin films on dielectric substrates that are commonly used in IR spectroscopy. The VSFG spectra on SiO2 and CaF2 exhibit notably different intensities for the F1u and Ag vibrational modes. This difference is attributed to different interfacial surface charges and C60/surface interactions. DFT calculations were performed to model the influence of a unidirectional electrostatic perturbation on the IR and Raman activities. The VSFG activities were then calculated for comparison to the interfacial second-order susceptibilities obtained from multilayer interference fitting of the experimental spectra. We find that the negative surface charge of CaF2 substrates causes a larger perturbation of fullerene than native silica surfaces, which leads to a stronger influence on the VSFG spectra.