We report on the surface-sensitive chemical analysis of organic insulating thin films using negative secondary ions (N-SIs) induced by C60 impacts in the medium energy range from several tens to several hundreds keV. The incident C60 energy dependence of emission yields of characteristic N-SIs for poly(methyl methacrylate) and charging effects on the N-SI mass spectra were investigated using time-of-flight SI mass spectrometry. Our results show that medium energy C60 impacts stably provide considerably high characteristic N-SI yields without charge compensation, and demonstrate that time-of-flight SI mass spectrometry with medium energy C60 impacts is advantageous for the highly-sensitive chemical analysis of organic insulators.