Typical tasks of a river monitoring network design include the selection of the water quality parameters, selection of sampling and measurement methods for these parameters, identification of the locations of sampling stations and determination of the sampling frequencies. These primary design considerations may require a variety of objectives, constraints and solutions. In this study we focus on the optimal river water quality monitoring network design aspect of the overall monitoring program and propose a novel methodology for the analysis of this problem. In the proposed analysis, the locations of sampling sites are determined such that the contaminant detection time is minimized for the river network while achieving maximum reliability for the monitoring system performance. Altamaha river system in the State of Georgia, USA is chosen as an example to demonstrate the proposed methodology. The results show that the proposed model can be effectively used for the optimal design of monitoring networks in river systems.