The emission spectrum of the b′3Σu−–X1Σg+ system between 3540–4375 Å and ascribed previously by Mrozowski and Santaram to the a3Σu+–X1Σg+ transition of the P2 molecule, has been photographed under high resolution. The rotational analysis of 7 bands has been carried out and allowed us to determine the rotational constants of the vibrational levels ν′ = 0, 1, and 2 as well as the spin splitting constants λ′ and γ′. The nature of the upper state has been identified as a 3Σu− state, the electronic transition being analogous to the Ogawa–Tanaka–Wilkinson system of N2.