In high-spin chemistry, random-orientation fine-structure (FS) electron spin resonance (ESR) spectroscopy entertains advantages as the most facile and convenient method to identify high-spin systems, as frequently reported in the literature. Random-orientation ESR spectroscopy applicable to organic high-spin entities can date back to the Wasserman and co-workers' attempt on the first spin-quintet dicarbene, m-phenylenebis-(phenylmethlene) (m-PBPM), in the 2-MTHF glass in 1963 and 1967, following their Successful work on randomly oriented triplet-state ESR spectroscopy. The FS ESR spectrum of m-PBPM in the 2-MTHF glass, however, has never fully been analyzed due to a peculiar line-broadening appearing at many canonical peaks. Organic high-spin spectra from most quintet dinitrenes also suffer from similar phenomena. Seemingly intrinsic line-diffusing or -broadening phenomena adversely affect the reliable determination of FS parameters for organic high-spin entities in rigid glasses. In high-spin chemistry, the line-broadening has been,in obstacle that masks key FS transitions in many cases. Thus, both the origin of the broadening and the comprehensive spectral analysis have been a long-standing issue. In this report, we examine the origin of the line-broadening of appearing in the FS ESR spectra, illustrated by a comprehensive spectral analysis for m-PBPM in the quintet ground state and the first-documented quintet-state dinitrene, m-phenylenebis(nitrene) (m-PBN) in the 2-MTHF glass. A complete analysis of the random-orientation FS spectra from m-PBPM diluted in the benzophenone crystal has shown that the g-anisotropy of m-PBPM is not prominent. Also the higher-order FS terms Such as (SiSj2)-S-2 group-theoretically allowed for S = 2 are not necessary in spite of the argument for a hydrocarbon-based tetraradical (S = 2) in the ground state. Our new approach to the line-broadening analysis invokes both exact analytical solutions for the resonance fields of canonical peaks and the magnetic-parameters gradient method. The D- and E-values of m-PBPM acquired by the spectral simulation in this Study give different molecular structures of the quintet dicarbene in the benzophenone crystal lattice (D = +0.0703(0) cm(-1), E = +0.0212(0) cm(-1)) and in the 2-MTHF glass (D = +0.0780(0) cm(-1), E = +0.0221(0) cm(-1)). Microscopic origins of the line-broadening observed for high-spin oligocarbenes or oligonitrenes generated by photolysis in organic glasses have been proposed.