Charge transfer was predicted in the Zn‐Ar system. We have shown experimentally the validity of this prediction and that in fact Ar+excites the Zn+ 2P3/2,1/2states. Moreover, we find that this process preferentially excites theJ= (1)/(2) state in this mixture. This is inferred from the behavior of the intensity ratio of the transition from these two states in correlation with the intensity of the 811.5‐nm line of Ari, where the latter is a measure for Ar ionization. Our model is based on the molecular states of Zn+Ar and Ar+Zn. The model displays a plausible curve crossings leading to the preference2P1/2excitation.