Detailed regions of excitation and emission wavelengths for extra virgin olive oil samples have been extracted from three dimensional front-face fluorescence spectra. Information was applied to establish a right-angle fluorescence procedure. A right-angle device was assembled and tested with simultaneous excitation from 200 to 400 nm and registration of the fluorescence signal emitted from 400 to 850 nm. A principal component analysis was performed on the signal ranging from 400 to 550 nm from spectra of olive oils officially categorized as extra virgin in order to model the expected variability of compounds related to oxidative processes. Such model was useful to monitor the spectral evolution of extra virgin olive oil samples acquired at retail markets, which were exposed to indirect light during 2 months, through the analysis of the effect on their scores. Three relevant peaks characterized such evolution, with local maxima at around 434 to 437, 464 to 469 and 510 to 518 nm. Polynomial relationship was found between the evolution of those peaks and that of the chlorophyll, at around 670 to 673 nm, with R2 values of 0.98 and 0.99.