Process monitoring and control methods during direct metal deposition (DMD) are used to ensure a consistent manufacturing quality of the process. In the optical regime, naturally occurring process emission provides therefore selective and specific element lines, which can be obtained by optical spectrometers. However, DMD processes are in the heat conduction regime and superimposed broad spectral emissions dominate the wavelength specific signals. The aim of this work is to investigate the occurrence of different elemental lines in DMD processes as well as deposition track cross-sectional dimensions. Therefore, experiments were simultaneously conducted by using a high-resolution spectrometer (resolution = approx. 47 pm FWHM at 522 nm and 55 pm FWHM at 407.5 nm) and a medium resolution spectrometer (resolution = 0.73 nm FWHM), which were coupled by a bifurcated optical fibre. A parameter study of 27 single track DMD experiments using Co-Cr-based (MetcoClad21) powder on low-alloyed tool steel C45W (1.1730) substrate material, varying laser power, scan velocity and powder feed rate was conducted. Series of spectra were obtained for all sets of parameters with a scan rate of 100 Hz. The individual wavelength spectrum was analysed and classified by an algorithm into two types. Type-A spectra, with specific element emission lines and Type-B spectra, without significant emission lines with mostly predominant thermal emission radiation. Each deposition track was coupled to cross-sectional dimensions, including height, welding depth and melted areas. In addition, certain elemental lines contained in Type-A spectra were verified by using data from the NIST atomic spectra database. The investigation indicates that the relative number of Type-A spectra with respect to the total quantity of spectra, correlates significant to the process parameters. All detected and identified element lines occurred to be non-ionised elements, especially Cr I, Fe I and Mn I lines were frequently observed.