A spectroscopic investigation of corona discharges in SF6/N2 gas mixtures has been undertaken using an optical multichannel analyser (OMA). A point-to-plane geometry has been used with point radii varying from 3 to 10 μm. Spectra are measured for high pressures ranging from 0.2 MPa up to 1.4 MPa and for different concentrations of SF6 in the gas mixture. The spectra in the 200–850 nm spectral range are mainly made of molecular bands, which is indicative of a low temperature discharge. It has been noted that SF6 emits in the region of 420 nm to 510 nm in positive and negative polarities, although in negative polarity the emission is weaker. For SF6/N2 mixtures, the main source of light emission is from N2. The resultant spectra are used to evaluate the rotational Tr and vibrational Tv temperatures of excited N2, Tr being considered, due to the high pressure, to be equal to the kinetic temperature Tkin in the corona discharge. Tr and Tv are determined by comparing the experimental spectrum of the second positive system ($C^{3}\Pi_{u}\to B^{3}\Pi_{g})$ of N2 and the simulated one, which is obtained using a convolution method. As expected, the results show that the measured rotational temperature Tr increases steadily with the mean discharge current, while its increase with gas pressure is less pronounced. The values of Tr are higher for the positive corona discharge than the negative and also for mixtures having higher amounts of SF6. In all conditions, we found $T_{v}>T_{r}$ and Tv is less sensitive to the variation of the current.