Emission from atomic copper and CuF is characterized in a pulsed dc discharge in CF4/O2/Ar with a copper electrode. Similar emission is seen from neat Ar discharges, provided that a F‐ (or H2O‐) containing plasma has been operated first. Near the electrode surface emissions from CuF and lower‐energy states of Cu are observed. In the bulk of the plasma, additional emission is seen from more energetic states of Cu at the end of the pulse. Lifetime and energy considerations suggest that much of the Cu emission seen in Ar plasmas may arise from collisions between argon metastables and some molecular species, such as CuF.