Due to elevated pressure, cold atmospheric pressure plasmas generate excimer species, which can emit highly energetic photons, thus transferring energy inside the discharge and to treated substrates. However, they are difficult to assess, as they are absorbed by air or window material. Here, we present a method to measure vacuum ultraviolet photons using a monochromator with an aerodynamic window. The emission spectra of a radiofrequency‐excited atmospheric plasma jet were analyzed for typical gas mixtures. The data indicate that helium excimers contribute notably to the excitation of molecular and atomic species. The emission intensities do not follow densities of ground‐state species, underlining the variety of excitation channels and the change of the electron energy distribution function under changing gas composition.