Direct metal deposition (DMD) can be used for the cladding of surfaces as well as repairing and additive manufacturing of parts and features. Process monitoring and control methods ensure a consistent quality during manufacturing. Monitoring by optical emission spectroscopy of the process radiation can provide information on process conditions and the deposition layer. The object of this work is to measure optical emissions from the process using a spectrometer and identify element lines within the spectra. Single spectra have been recorded from the process. Single tracks of Co-based powder (MetcoClad21) were clad on an S235 base material. The influence of varying process parameters on the incidence and intensity of element lines has been investigated. Moreover, the interactions between the laser beam, powder jet, and substrate with regard to spectral emissions have been examined individually. The results showed that element lines do not occur regularly. Therefore, single spectra are sorted into spectra including element lines (type A) and those not including element lines (type B). Furthermore, only non-ionised elements could be detected, with chromium appearing frequently. It was shown that increasing the laser power increases the incidence of type A spectra and the intensity of specific Cr I lines. Moreover, element lines only occurred frequently during the interaction of the laser beam with the melt pool of the deposition layer.