A deterministic model was developed to predict pollutant mass first flush and to utilize it for better design of best management practices (BMPs) that focus on treating the first flush. The model used the kinematic wave equation to calculate flow and mass transport, and erosion equations to calculate pollutant concentrations, which were assumed to be from a short and a long term source. The model parameters were calibrated with a parameter estimation procedure using three years' monitoring data from a highway runoff site in west Los Angeles. The simulation results showed that there exists an optimum watershed size to maximize first flush. Contours of watershed length, developed from simulations for different conditions of rainfall and watershed geometry, can be used to design runoff collection systems for highways and parking lots to maximize first flush.