BN molecules, isoelectronic with C2, are produced by laser vaporization of boron nitride and trapped in solid neon. Through Fourier-transform absorption and laser-induced fluorescence spectra, three new electronic states are observed. Unlike C2, BN has a triplet ground state (X 3Π), but with an exceedingly low-lying singlet (a 1∑+) state with 15 cm−1<Te<182 cm−1.