In this study, we explored the correlation between fluctuated waveform tails under both positive and negative impulse voltages and their corresponding spectral lines during millisecond observations of arc discharge. We examined impulse voltages in ±100, ±125, and ±150 kV across 3, 3.5, and 4 cm gaps using spectroscopic analysis focused on oxygen excitations. Six selected spectra in ±100, ±125, and ±150 kV at 3.5 cm and two negative spectra of −100 kV at 3 and 4 cm were analyzed by identifying spectral lines in the wavelength range of 200–900 nm. The results revealed a correlation between the fluctuated waveform tails and spectral lines in positive voltage discharges, which were almost similar, while in negative voltage discharges, this correlation was found only in −100 kV at 3 and 4 cm. We concluded that during the spark phase for both positive and negative voltage discharges, symmetrical fluctuation in the waveform tails was observed after breakdown time, especially above the voltage level of the recombination phase. This suggested the presence of energetic oxygen excited states in the 200–400 nm range, with higher peak intensity than the O I line at 777.417 nm, observed in most positive impulse voltage discharges and at −100 kV with 3 and 4 cm gaps, contributing to rapid breakdown.