Plasmonic interactions between two metallic tips are dynamically studied in a supercontinuum dark-field microscope and the transition between coupled and charge-transfer plasmons is directly observed in the sub-nm regime. Simultaneous measurement of the dc current, applied force, and optical scattering as the tips come together is used to determine the effects of conductive pathways within the plasmonic nano-gap. Critical conductances are experimentally identified for the first time, determining the points at which quantum tunnelling and conductive charge transport begin to influence plasmon coupling. These results advance our understanding of the relationship between conduction and plasmonics, and the fundamental quantum mechanical behaviours of plasmonic coupling.The authors would like to acknowledge Nanotools GmbH for their contributions and support to this project. We acknowledge EPSRC Grants No. EP/G060649/1, No. EP/L027151/1, and No. EP/K028510/1, ERC Grant No. LINASS 320503, and Ikerbasque. RWB thanks Queens’ College, Cambridge and the Royal Commission for the Exhibition of 1851 for financial support.This is the final version of the article. It first appeared from Nature Publishing Group via http://dx.doi.org/10.1038/srep3298