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This paper provides a novel approach to determining optimal sampling locations for chlorine decay model calibration. Three questions are investigated: (1) What is the minimum number of chlorine sample locations needed? (2) How many combinations of sampling locations are available? (3) What is the optimal location combination? To answer the first two questions, the mathematical expressions of the chlorine concentrations between any two sampling locations are developed and sampling point relationship matrices are generated, then a mixed integer programming (MIP) algorithm is developed. Once obtained, the solutions to the first two questions are used to calculate the chlorine decay wall reaction coefficients and sensitivity matrix of chlorine concentration to wall reaction coefficients; then, sampling location combinations achieved in the second question are sorted using a D-optimality algorithm. The model frame is demonstrated in a case study. [ABSTRACT FROM AUTHOR]