The underlying natural relationship between conductivity and alkalinity was used to identify surface water quality monitoring sites that are in a ‘reference’ or minimally disturbed condition. Data from over 40,500 freshwater samples from 1,230 sites were combined for the time period of 2005–2015 from various federal, provincial, and joint federal–provincial/territorial freshwater monitoring programs (e.g., Freshwater Quality Monitoring and Surveillance Program, Ontario's Provincial Water Quality Monitoring Network). Of the samples, 30,347 provided conductivity and alkalinity data. Surface water samples with a measured conductivity that deviated (by more than 41 μS/cm) from the predicted conductivity calculated from the sample's alkalinity were deemed to be non-representative of a reference condition, while samples within 41 μS/cm of the predicted value were deemed representative of a reference condition. The 41 μS/cm cutoff value was determined using signal detection theory. The conductivity–alkalinity model was validated through a comparison with land cover data by demonstrating that samples identified as ‘reference’ were typically from catchments that had minimal anthropogenic disturbances. The proposed approach provides a rapid means of evaluating the reference condition of a watercourse, and of identifying data that provide an estimate of reference condition.