This supplementary material provides detailed information on local heating and Raman thermometry in a single molecule. The study investigates the anti-Stokes and Stokes Raman intensities under different tunneling conditions, revealing that the anti-Stokes signals become visible as the tunneling current increases, indicating heating effects. The electronic Raman scattering (ERS) is identified as the main source of the background in anti-Stokes Raman spectra, with the effective electronic temperature (Te) increasing with tunneling conditions, indicating inelastic tunneling-induced heating. The effective electronic temperature of the silver tip is distinct from the effective temperature of molecular vibrations. The calibration factors for the anti-Stokes-to-Stokes ratios for different vibrational modes are estimated by measuring plasmonic emission spectra under various conditions. The calibration factors are derived from the STML spectra, which reflect the frequency-dependent plasmonic resonance properties. The calibration factors are used to analyze the Raman peaks in the main text. The non-equilibrium Green's function (NEGF) theory is applied to model heat dissipation in molecular junctions, considering phonon populations and electron-phonon interactions. The effective temperature of the molecule is determined by energy conservation across vibrational modes. The decomposition of C60 upon heating is analyzed through Raman and STM measurements, showing structural changes with the formation of a C58 structure. The tip-molecule distances are estimated based on tunneling and contact conditions, while thermal drift is minimized for TERS mapping experiments. The study also includes figures and tables illustrating the experimental setup, Raman spectra, and calibration factors, as well as references to supporting literature. The results demonstrate the feasibility of using Raman thermometry for single-molecule studies, with implications for nanoscale thermal management and molecular electronics.This supplementary material provides detailed information on local heating and Raman thermometry in a single molecule. The study investigates the anti-Stokes and Stokes Raman intensities under different tunneling conditions, revealing that the anti-Stokes signals become visible as the tunneling current increases, indicating heating effects. The electronic Raman scattering (ERS) is identified as the main source of the background in anti-Stokes Raman spectra, with the effective electronic temperature (Te) increasing with tunneling conditions, indicating inelastic tunneling-induced heating. The effective electronic temperature of the silver tip is distinct from the effective temperature of molecular vibrations. The calibration factors for the anti-Stokes-to-Stokes ratios for different vibrational modes are estimated by measuring plasmonic emission spectra under various conditions. The calibration factors are derived from the STML spectra, which reflect the frequency-dependent plasmonic resonance properties. The calibration factors are used to analyze the Raman peaks in the main text. The non-equilibrium Green's function (NEGF) theory is applied to model heat dissipation in molecular junctions, considering phonon populations and electron-phonon interactions. The effective temperature of the molecule is determined by energy conservation across vibrational modes. The decomposition of C60 upon heating is analyzed through Raman and STM measurements, showing structural changes with the formation of a C58 structure. The tip-molecule distances are estimated based on tunneling and contact conditions, while thermal drift is minimized for TERS mapping experiments. The study also includes figures and tables illustrating the experimental setup, Raman spectra, and calibration factors, as well as references to supporting literature. The results demonstrate the feasibility of using Raman thermometry for single-molecule studies, with implications for nanoscale thermal management and molecular electronics.