A multitude of organic transformations catalyzed by dirhodium(II) (Rh-2) complexes are thought to proceed via the intermediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observation. Herein, we report the generation of a metastable Rh-2-carbenoid intermediate supported by a donor-acceptor carbene fragment. This intermediate is stable for a period of similar to 20 hours in chloroform solution at 0 degrees C, allowing for an exploration of its physical and chemical properties. The Rh=C bond, characterized by vibrational and nuclear magnetic resonance spectroscopy, extended x-ray absorption fine structure analysis, and quantum-chemical calculations, has weak sigma and pi components. This intermediate performs stoichiometric cyclopropanation and C-H functionalization reactions to give products that are identical to those obtained from analogous Rh-2 catalysis.