In-water biogeochemical constituents and bio-optical properties of the St-Lawrence Gulf and Estuary were monitored during 5 cruises conducted between 1997-2001 accross different seasons. Measured inherent optical properties (IOPs) included vertical profiles of the absorption and attenuation coefficients and the volume scattering function as well as absorption by particles, non-algal particles, phytoplankton and coloured dissolved organic matter (CDOM). Apparent Optical parameters (AOPs) included vertical profiles of the upwelling radiance and downwelling irradiance. The spectral shape of the major IOPs like absorption by phytoplankton, CDOM and non-algal particles as well as the particulate backscattering were parameterized using conventional models and adaptations of conventional models. Descriptive statistics of each variable in the collected dataset were analysed and compared with previous findings in the literature. The optical coherence of the measurements was verified using a radiative transfer closure approach. A complete set of IOP cross-sections for optically significant biogeochemical variables were generated. The magnitude and the spatial, temporal and spectral variation exhibited by the optically significant inwater biogeochemical constituents as well as the bio-optical parameters was consistent with our current knowledge of the ecosystem. The variation of the bio-optical parameters throughout the seasons was also coherent with our expectations. All the measured and derived parameters were found to vary within the ranges reported in the literature. Evidence was presented wherein the Gulf waters, which are usually considered as case I waters could also behave like case II waters. Moreover, spectral signatures exhibited by the IOPs and AOPs were coherent with the variation detected in the concentrations of the measured (optically significant) constituents. The extracted IOP cross-sections were consistent with the results of similar studies previously performed and could eventually be used in the estimation of the biogeochemical constituent concentrations given the related component IOPs. First-order radiative transfer closure was achieved; this underscored the validity of our experimental dataset based on considerations of higher level, integrative, physics. We argue that the current data collection campaign succeeded as a comprehensive framework for describing the behavior of the St-Lawrence bio-optical provinces within the context of remote sensing objectives. This bio-optical dataset should provide the basis for the development of a rigorous, satellite-based, remote sensing algorithm for the retrieval of near surface chlorophyll, fine-tuned to the local characteristics of the St-Lawrence system.