Passive samplers accumulate organic contaminants at rates that depend on in-field exposure conditions such as freshwater flow velocity, water temperature and water quality. Time-weighted average concentrations can be determined by using a correction process such as the performance reference compound (PRC) method. This study presented a new approach to predict the accumulation behavior of pesticides in polydimethylsiloxane-coated stir bars under different exposure conditions and assign a specific PRC to each pesticide for quantitative purposes. We used an experimental design with eight simultaneous accumulation kinetics of 13 pesticides and elimination kinetics of three PRC candidates run in a flow-through system to determine the effects of flow velocity, water temperature and dissolved organic matter on the kinetic constants. We identified the parameters that had a significant effect on the accumulation of each pesticide and assigned a PRC candidate to each pesticide. We then used a discriminant function analysis to find the parameters that had a significant effect on accumulation of the 13 pesticides via their physical-chemical properties and to predict through a stochastic approach the parameters for seven other pesticides. This approach provides a better framework for identifying a PRC than conventional methods to determine unbiased concentrations in future monitoring efforts.