Shedding new light on the right combination of catalysts: A new dual catalytic system for efficient CH functionalization was developed. The appropriate choice of two metal catalysts allows the oxidative alkynylation of tertiary amines under mild and sustainable reaction conditions. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.