Recent shifts in water quality and food web characteristics driven by anthropogenic impacts on the Laurentian Great Lakes warranted an examination of pelagic primary producers as tracers of environmental change. The distributions of the 263 common phytoplankton taxa were related to water quality variables to determine taxon-specific responses that may be useful in indicator models. A detailed checklist of taxa and their environmental optima are provided. Multivariate analyses indicated a strong relationship between total phosphorus (TP) and patterns in the diatom assemblages across the Great Lakes. Of the 118 common diatom taxa, 90 (76%) had a directional response along the TP gradient. We further evaluated a diatom-based transfer function for TP based on the weighted-average abundance of taxa, assuming unimodal distributions along the TP gradient. The r2 between observed and inferred TP in the training dataset was 0.79. Substantial spatial and environmental autocorrelation within the training set of samples justified the need for further model validation. A randomization procedure indicated that the actual transfer function consistently performed better than functions based on reshuffled environmental data. Further, TP was minimally confounded by other environmental variables, as indicated by the relatively large amount of unique variance in the diatoms explained by TP. We demonstrated the effectiveness of the transfer function by hindcasting TP concentrations using fossil diatom assemblages in a Lake Superior sediment core. Passive, multivariate analysis of the fossil samples against the training set indicated that phosphorus was a strong determinant of historical diatom assemblages, verifying that the transfer function was suited to reconstruct past TP in Lake Superior. Collectively, these results showed that phytoplankton coefficients for water quality can be robust indicators of Great Lakes pelagic condition. The diatom-based transfer function can be used in lake management when retrospective data are needed for tracking long-term degradation, remediation and trajectories.