In this study, the B 1Π excited state of NaH has been experimentally studied for the first time. Pulsed laser-induced fluorescence excitation spectroscopy was used to investigate the B 1Π electronic state of NaH. A total of 48 ro-vibronic transitions were observed, including within the B–X (0–0) and B–X (0–1) transition bands. Only one B-state vibrational level was identified, and a series of PQR lines, with eight e-parity and eight f-parity sublevels (v′ = 0, J′ = 1–8), were assigned. The level assignment was supported by a comparison of the experimental line positions with the ab initio calculations, the dispersed laser-induced fluorescence spectrum of the NaH B 1Π → X 1∑+ emission, and the V-type optical–optical double resonance spectra. The Dunham-type coefficients, the mean internuclear distance, the harmonic vibrational frequency ω, and the dissociation energies D 0 and D e of the B 1Π state were determined.