A widely applicable fiber-optic UV-vis method to determine the spectra of in situ generated redox products and intermediates at or near an electrode surface is described mathematically and implemented experimentally. The quantitative spectral information obtained gives extinction coefficients (absorptivities) as a function of wavelength, requires no arbitrary subtraction of the spectrum of the starting material, and is relatively insensitive to path length and concentration during the spectroelectrochemical measurements. We demonstrate proof-of-concept of this methodology by reproducing the expected spectrum of the ferrocenium ion from electrooxidation of ferrocene in MeCN, and by reproducing the spectrum that reveals π-radical cation formation from the electrooxidation of (T(p-OMe)PP)Co(NO) ((T(p-OMe)PP = 5,10,15,20-tetra(p-methoxyphenyl)porphyrinato dianion). Importantly, we demonstrate its use for the facile detection of unstable redox products not previously detected by current spectroelectrochemical methods. We obtain, for the first time, the experimental UV-vis spectrum of the short-lived fac-[(dppe)Mn(CO)(3)Br](+) cation, a hitherto uncharacterized intermediate that forms during the archetypal redox-induced fac-to-mer isomerization of (dppe)Mn(CO)(3)Br (dppe = diphenylphosphinoethane). Spectral features of the Mn-containing species have been verified by comparison to theoretical spectra calculated by time-dependent density functional theory methods.