The plasma emission pre-peaks of many atomic and ionic spectral lines of Cu and Ar were systematically investigated in a Grimm-type pulsed glow discharge (PGD). To register the pre-peaks with sufficient time resolution, a monochromator with photomultiplier detection was used. When the applied power exceeded a specific threshold, pre-peaks were found in all spectral lines investigated, and it was revealed that the electrical pre-peak was the cause of the atomic emission pre-peak. The form and intensity of the pre-peak radiation were, however, found to be different for different atomic emission lines. The excitation energy of the upper energy level of the atomic line transition, and factors related to recombination and self-absorption, were found to affect the emission pre-peak. Pre-peaks observed when using pulsed DC and pulsed radio-frequency power were compared. This investigation provides insight into best practice when selecting spectral lines most suitable for analytical spectrometry using PGD.