We report the direct and accurate spectroscopic quantification of the inverted singlet-triplet gap in 1,3,4,6,9b-pentaazaphenalene. This measurement is achieved by directly probing the lowest singlet and triplet states via high-resolution cryogenic anion photoelectron spectroscopy. The assignment of the first excited singlet state is confirmed by visible absorption spectroscopy in an argon matrix at 20 K. Our measurements yield an inverted singlet-triplet gap with ΔEST= -0.047(7) eV. The accurate quantification of the singlet-triplet gap presented here allows for direct evaluation of various computational electronic structure methods and highlights the critical importance of the proper description of the double excitation character of these electronic states. Overall, this study validates the idea that despite Hund's multiplicity rule, useful organic chromophores can have inherently inverted singlet-triplet gaps.