The optical spectrum of the PtN radical has been observed directly for the first time. The strongest band system [(0,0) bandhead at 18 591 cm−1] displays an unusual ‘‘perpendicular ΔΩ=0’’ perturbation which gives rise to strong intensity cancellation effects. Although a 4Σ− ground state was expected for PtN, we have assigned the ground state as 2Πr; a 4Σ− assignment is not consistent with our observations. We have used arguments based on both molecular orbital theory and atomic-ion-in-molecule theory to explain the observed ground state symmetry in light of the observed hyperfine structure. Four electronic bands involving a total of six Hund’s case (c) ‖v,Ω〉 substrates have been rotationally analyzed, and many more bands have been observed at lower resolution. The ground state was found to have Ω=0.5 and its principal constants are Be=0.455 708(5) cm−1, αe=0.003 448 1(1) cm−1, spin–rotation constant γ0=0.061 26(7) cm−1, ωe=947.0(5) cm−1, and ωexe=5.0(5) cm−1. Two other Ω states were observed at low energies—an Ω=1.5 state at Te=2 985.665(2) cm−1, with B0=0.445 233(8) cm−1, q=1.522(5)×10−6 cm−1, ωe=901(1) cm−1, and ωexe=8(1) cm−1, and another Ω=0.5 state with Te undetermined and other constants remarkably similar to those of the ground state (B0=0.453 07(6) cm−1, γ0=0.062 02(4) cm−1, ωe=947(1) cm−1, and ωexe=5(1) cm−1).