The variability of inherent optical properties is investigated in the ultra-oligotrophic waters of the Mediterranean Sea sampled during the BOUM experiment performed during early summer 2008. Bio-optical relationships found for ultra-oligotrophic waters of the three anticyclonic gyres sampled significantly depart from the mean standard relationships provided for the global ocean, confirming the peculiar character of these Mediterranean waters. These optical anomalies are diversely related to the specific biological and environmental conditions occurring in the studied ecosystem. Specifically, the surface specific phytoplankton absorption coefficient exhibits values lower than those expected from the general relationships mainly in relation with a high contribution of relatively large sized phytoplankton. Conversely, the particulate backscattering coefficient, b(bp), values are much higher than the mean standard values for a given chlorophyll-a concentration, TChl-a. This feature can presumably be related to the relevant influence of highly refractive submicrometer particles of Saharan origin in the surface layer of the water column. The present measurements also show that the Mediterranean Sea is greener than TChl-a alone indicates, as already stressed in previous studies. This color anomaly is partly explained by the estimated colored dissolved organic matter and submicrometer particles absorption coefficients, and to a greater extent by the high b(bp)/TChl-a values assuming that these particles backscatter light similarly in the green and blue parts of the visible spectrum. The diel variation of both the particulate matter attenuation and backscattering coefficients were also investigated specifically. Despite some differences in the timing and the magnitude of the daily oscillations found for these optical parameters, potential for the backscattering coefficient daily oscillation to be used, similarly to that for the attenuation coefficient, as a proxy for estimating carbon community production budget has been highlighted for the first time. This result is particularly relevant for present and future geostationary spatial ocean color missions.