The geochemical signature of freshwater streams can be used to determine the extent and nature of modification to stream water geochemistry due to urban development. This approach used the Gibbs (1970) diagram as a model for evaluation of changes to ionic composition linked to urban development. In this multi-year study, the geochemistry of 21 waterways in the Georges River catchment, Sydney, were monitored and compared with the level of urban development as measured by sub-catchment imperviousness and directly connected imperviousness. The results reflect a strong relationship between the intensity of sub-catchment urban development and stream geochemistry. All major geochemical attributes increased with escalating levels of urban development. The largest increase was for bicarbonate, which increased 18 times from a mean of 6.4mgL-1 at non-urban streams to a mean of 118mgL-1 at urban streams. Similarly, mean concentrations of calcium increased by 14 times (from 2 to 27.9mgL-1). Mean salinity was enriched in the most urban streams, compared with non-urban streams, by more than 6 times. We attribute this, in part, to the influence of urban geology, notably concrete stormwater infrastructure. Changes in stream geochemistry due to urban development are an important element of the urban stream syndrome.