In this work, charge‐transfer mechanism of surface‐enhanced resonance Raman scattering (SERRS) spectroscopy of pyrazine absorbed on Ac@Au7 clusters is theoretically investigated, and the coupling effect between the nanoparticles is especially concerned. First, the contributions of coupling effect to surface‐enhanced Raman scattering (SERS) are compared between the ground‐state nanoparticles. Second, the visualization of charge transfer provides evidence for the coupling effect on the charge‐transfer enhancement mechanism of SERRS spectroscopy. The theoretical results show that the coupling effect on charge‐transfer mechanism of SERRS can significantly enhance the intensity of SERS spectra up to about 6 × 105 times. The different coupling ways not only result in different degree of charge transfer on electronic transitions, but also cause different intensity of charge‐transfer absorption peaks. Both of them strongly influence the enhancement of charge‐transfer mechanism of SERRS. This study promotes the understanding of charge‐transfer enhancement mechanism of SERRS for ultrasensitive Raman spectral analysis at nanoscale. Copyright © 2017 John Wiley & Sons, Ltd.