The strongly perturbed 1Π–X1Σ+ system of C80Se has been observed in the emission spectrum of a high frequency discharge through selenium and carbon traces in a neon atmosphere. The analysis of five bands yields, for the molecular constants of the ground state, the values Be″ = 0.5750 cm−1, [Formula: see text], αe″ = 0.00379 cm−1, re″ = 1.676 Å, ΔG″(1/2) = 1025.64 cm−1, and ΔG″(3/2) = 1015.92 cm−1. The numerous perturbations in the 1Π state prohibit the simple evaluation of the constants of the perturbed state and of the perturbing ones.