Three singlet–triplet transitions, b1Σ+−X3Σ−, c1Π–X3Σ−, and d1Π–X3Σ−, and two 3Π–X3Σ− transitions attributed to the molecule AsF, have been found in the regions 1900–2300 Å and 7000–7400 Å. The vibrational analysis for the observed systems and the rotational analysis of the singlet–triplet transitions are complete. The analysis shows that the ground state X3Σ− belongs to Hund's case c with a spin coupling constant λ of about 70 cm−1. The analysis of the observed transitions and a discussion of the relative position and molecular configurations of the observed states are presented.