This supplementary material provides detailed experimental and theoretical analyses supporting the findings in the main text of the article "Local heating and Raman thermometry in a single molecule" by Qiushi Meng et al. The content includes: 1. **Comparisons of Anti-Stokes and Stokes Raman Intensities**: The intensities of anti-Stokes and Stokes Raman signals are influenced by bias voltages and tunneling currents. At low tunneling conditions, anti-Stokes signals are absent, while at moderate and high tunneling conditions, they become visible and strong due to heating effects. 2. **Analysis of Electronic Raman Scattering (ERS)**: The background in anti-Stokes Raman spectra is attributed to ERS from the silver tip or substrate. The ERS profile is fitted using a Fermi-Dirac distribution function to extract effective electronic temperatures, which increase from 526 K to 1084 K as tunneling conditions change. 3. **Estimation of Calibration Factors**: Calibration factors for anti-Stokes-to-Stokes ratios for different vibrational modes are estimated by measuring plasmonic emission spectra under various tunneling conditions. These factors are crucial for accurate vibrational mode identification in TERS data. 4. **Non-equilibrium Green's Function (NEGF) Theory**: The NEGF theory is used to describe heat dissipation in molecular junctions, providing a theoretical framework for understanding the phonon population and effective temperature of the molecule. 5. **Possible Structure for Decomposition Product of C60**: The chemical structure of the decomposition product of C60 is proposed to be C58, with a heptagon formed by the loss of two carbon atoms from the central hexagon. This structure is supported by Raman and STM topographic analyses. 6. **Estimation of Tip–Molecule Distances**: The distances between the tip and the molecule are determined by measuring tunneling currents and conductance as a function of tip displacement. 7. **Measurement of Thermal Drift**: Thermal drift during TERS mapping experiments is minimized by waiting for thermal stabilization and applying drift compensation, with measurements showing negligible drift over the acquisition time. The supplementary material also includes figures and tables that provide visual and numerical support for the discussed phenomena and analyses.This supplementary material provides detailed experimental and theoretical analyses supporting the findings in the main text of the article "Local heating and Raman thermometry in a single molecule" by Qiushi Meng et al. The content includes: 1. **Comparisons of Anti-Stokes and Stokes Raman Intensities**: The intensities of anti-Stokes and Stokes Raman signals are influenced by bias voltages and tunneling currents. At low tunneling conditions, anti-Stokes signals are absent, while at moderate and high tunneling conditions, they become visible and strong due to heating effects. 2. **Analysis of Electronic Raman Scattering (ERS)**: The background in anti-Stokes Raman spectra is attributed to ERS from the silver tip or substrate. The ERS profile is fitted using a Fermi-Dirac distribution function to extract effective electronic temperatures, which increase from 526 K to 1084 K as tunneling conditions change. 3. **Estimation of Calibration Factors**: Calibration factors for anti-Stokes-to-Stokes ratios for different vibrational modes are estimated by measuring plasmonic emission spectra under various tunneling conditions. These factors are crucial for accurate vibrational mode identification in TERS data. 4. **Non-equilibrium Green's Function (NEGF) Theory**: The NEGF theory is used to describe heat dissipation in molecular junctions, providing a theoretical framework for understanding the phonon population and effective temperature of the molecule. 5. **Possible Structure for Decomposition Product of C60**: The chemical structure of the decomposition product of C60 is proposed to be C58, with a heptagon formed by the loss of two carbon atoms from the central hexagon. This structure is supported by Raman and STM topographic analyses. 6. **Estimation of Tip–Molecule Distances**: The distances between the tip and the molecule are determined by measuring tunneling currents and conductance as a function of tip displacement. 7. **Measurement of Thermal Drift**: Thermal drift during TERS mapping experiments is minimized by waiting for thermal stabilization and applying drift compensation, with measurements showing negligible drift over the acquisition time. The supplementary material also includes figures and tables that provide visual and numerical support for the discussed phenomena and analyses.